TW201900413A - Polyimide film and laminate of inorganic substrate - Google Patents
Polyimide film and laminate of inorganic substrate Download PDFInfo
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- TW201900413A TW201900413A TW107118286A TW107118286A TW201900413A TW 201900413 A TW201900413 A TW 201900413A TW 107118286 A TW107118286 A TW 107118286A TW 107118286 A TW107118286 A TW 107118286A TW 201900413 A TW201900413 A TW 201900413A
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- B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
- B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
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- H01L21/6835—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere for supporting or gripping using temporarily an auxiliary support
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Abstract
Description
本發明關於聚醯亞胺膜與玻璃等無機基板之疊層體,更詳細而言,係關於一種聚醯亞胺膜及無機基板之疊層體,其藉由將聚醯亞胺膜疊層於無機基板,以暫時支持可撓性聚醯亞胺膜,並藉由在聚醯亞胺膜上製造加工電子器件等功能元件後,將聚醯亞胺膜從無機基板剝離,而用於製造將聚醯亞胺膜作為基板之可撓性功能元件。The present invention relates to a laminated body of a polyimide film and an inorganic substrate such as glass. More specifically, the present invention relates to a laminated body of a polyimide film and an inorganic substrate. The inorganic polyimide film is temporarily supported on the inorganic substrate, and after the functional elements such as electronic devices are manufactured and processed on the polyimide film, the polyimide film is peeled from the inorganic substrate for manufacturing. A polyimide film is used as a flexible functional element of the substrate.
近年來,以半導體元件、MEMS元件、顯示器元件、穿戴式感測器等功能元件之輕量化、小型・薄型化、可撓化為目的,人們已積極開發在高分子膜上形成該等元件的技術。亦即,作為諸如資訊通訊設備(播送設備、移動無線電、行動通訊設備等)、雷達、高速資訊處理裝置等之電子零件之基材的材料,以往係使用具有耐熱性且亦能應對資訊通訊設備之信號頻帶之高頻化(達GHz帶)的陶瓷,但陶瓷沒有可撓性且亦難薄型化,故存在可適用之領域受限的缺點,因此最近係使用高分子膜作為基板。In recent years, in order to reduce the weight, miniaturization, thinness, and flexibility of functional elements such as semiconductor elements, MEMS elements, display elements, and wearable sensors, people have actively developed methods to form these elements on polymer films. technology. That is, as a base material of electronic parts such as information communication equipment (broadcasting equipment, mobile radio, mobile communication equipment, etc.), radar, high-speed information processing equipment, etc., conventionally, it is heat-resistant and can also handle information communication equipment Ceramics with high frequency (up to GHz band) in the signal frequency band, but ceramics are not flexible and difficult to be thinned, so there is a disadvantage that the applicable field is limited. Therefore, polymer films have recently been used as substrates.
當在高分子膜表面形成功能元件時,宜藉由利用了高分子膜之特性即可撓性的所謂卷對卷(Roll-to-Roll)處理進行加工較理想。但,在半導體產業、MEMS產業、顯示器產業等業界,至今為止已經構建了將晶圓為主或玻璃基板為主等之剛性平面基板作為對象的處理技術。因此,為了利用現有的基本架構在高分子膜上形成功能元件,有人使用如下處理:將高分子膜貼合於例如玻璃板、陶瓷板、矽晶圓、金屬板等由無機物構成之剛性支持體,並在其上形成所期望之元件,然後從支持體剝離。When forming a functional element on the surface of a polymer film, it is desirable to process it by a so-called roll-to-roll process that can be flexible by utilizing the characteristics of the polymer film. However, in the semiconductor industry, the MEMS industry, the display industry and other industries, processing technologies have been constructed that target rigid flat substrates such as wafers or glass substrates. Therefore, in order to form a functional element on a polymer film using the existing basic structure, some people use the following process: bonding the polymer film to a rigid support made of an inorganic substance such as a glass plate, a ceramic plate, a silicon wafer, a metal plate, etc. , And the desired element is formed thereon, and then peeled from the support.
另一方面,將用於功能元件之導體材料、絕緣體材料、半導體材料等形成為高分子膜狀時,大多利用真空薄膜法、厚膜法等於形成程序中加熱。一般該等材料使用高溫處理時會展現良好的特性。故,要求在已將高分子膜貼合於由無機物構成之支持體的狀態具有耐熱性。但,多數情況下,將高分子膜利用黏接材貼附於支持體時,由於黏接材之耐熱性低,往往會產生步驟上的不便。On the other hand, when a conductive material, an insulator material, a semiconductor material, or the like used for a functional element is formed into a polymer film, a vacuum thin film method or a thick film method is often used for heating in a forming process. Generally, these materials exhibit good characteristics when subjected to high temperature processing. Therefore, heat resistance is required in a state where a polymer film is bonded to a support made of an inorganic substance. However, in many cases, when a polymer film is attached to a support using an adhesive material, the heat resistance of the adhesive material is low, which often causes inconvenience in steps.
由於欠缺將高分子膜貼附於無機基板的耐熱黏接方式,該用途中已知有如下技術:將高分子溶液或高分子之前驅體溶液塗布於無機基板上,在支持體上使其乾燥、硬化而膜化,並使用於該用途。進一步,為了使剝離容易,有人提出形成多層並將一部分層使用作犧牲層的技術、或將黏接/剝離功能與膜物性予以功能分離的技術等(專利文獻1~3)。 利用該方式獲得之高分子膜脆且容易斷裂,故形成在高分子膜表面之功能元件從支持體剝離時往往會被破壞。特別是將大面積的膜從支持體剝離的情形極其困難,根本無法獲得工業上實用的產率。鑒於如此之情況,作為用於形成功能元件的高分子膜與支持體之疊層體,有人提案將耐熱性優異、強韌且可薄膜化之聚醯亞胺膜藉由矽烷偶聯劑貼合於由無機物構成之支持體(無機層)而成的疊層體(專利文獻4~5)。Due to the lack of a heat-resistant adhesion method for attaching a polymer film to an inorganic substrate, the following technology is known in this application: a polymer solution or a polymer precursor solution is coated on an inorganic substrate and dried on a support. , Harden into a film, and use it for this purpose. Further, in order to facilitate peeling, a technique of forming a plurality of layers and using a part of the layers as a sacrificial layer, or a technique of functionally separating the adhesion / peeling function from the film physical properties has been proposed (Patent Documents 1 to 3). The polymer film obtained by this method is brittle and easily broken, so functional elements formed on the surface of the polymer film are often destroyed when they are peeled from the support. In particular, it is extremely difficult to peel a large-area film from a support, and an industrially practical yield cannot be obtained at all. In view of this situation, as a laminate of a polymer film and a support for forming a functional element, it has been proposed that a polyimide film having excellent heat resistance, a toughness, and a thin film can be bonded by a silane coupling agent. A laminated body formed on a support (inorganic layer) made of an inorganic substance (Patent Documents 4 to 5).
該等疊層體之高分子膜面實際上存在各種缺點,功能性元件製造的產率低。高分子膜本身有傷痕等缺點時,需改善高分子膜的品質。高分子膜之表面附著有異物時,可同時進行步驟之潔淨化與高分子膜表面之清潔而對應。但,即便使用高品質之高分子膜,並進一步進行清潔,仍往往有缺點殘留於高分子膜面,功能性元件製造的產率無法改善。 [先前技術文獻] [專利文獻]The polymer film surfaces of these laminates actually have various disadvantages, and the production yield of functional devices is low. When the polymer film itself has flaws such as scratches, it is necessary to improve the quality of the polymer film. When foreign matter adheres to the surface of the polymer film, the steps of cleaning can be performed simultaneously with the cleaning of the surface of the polymer film. However, even if a high-quality polymer film is used and further cleaning is performed, defects often remain on the polymer film surface, and the yield of functional element manufacturing cannot be improved. [Prior Art Literature] [Patent Literature]
[專利文獻1]日本特開2016-120629號公報 [專利文獻2]日本特開2016-120630號公報 [專利文獻3]日本專利4834758號公報 [專利文獻4]日本特開2010-283262號公報 [專利文獻5]日本特開2011-11455號公報[Patent Document 1] JP 2016-120629 [Patent Document 2] JP 2016-120630 [Patent Document 3] JP Patent 4834758 [Patent Document 4] JP 2010-283262 [ Patent Document 5] Japanese Patent Application Laid-Open No. 2011-11455
[發明所欲解決之課題][Problems to be Solved by the Invention]
本案發明人等為了改善製造產率而進行努力研究的結果,發現功能性元件之製造產率低的原因之一在於泡罩。將高分子膜貼合於表面平滑且剛性的無機基板(以下,主要針對使用玻璃板作為無機基板之代表例的情況進行說明。)時,在高分子膜與玻璃板之間夾有異物的情況,以異物作為支柱高分子膜之一部分從玻璃板浮起成為帳蓬(tent)狀,高分子膜與玻璃板之間產生空隙,而產生膜表面變凸的缺點。此種缺點係泡罩缺點(有時亦簡稱為泡罩、或泡(bubble)、隆起、氣泡。)。 將高分子膜與無機基板藉由相對較厚之黏接劑層貼合時,異物會被埋在黏接材層中,故相對不易產生泡罩。但,黏接材層較薄的情況,尤其異物之高度大於黏接材層時,會產生泡罩。As a result of diligent research by the present inventors to improve the production yield, it was found that one of the reasons for the low production yield of the functional element is the blister. When a polymer film is bonded to an inorganic substrate with a smooth and rigid surface (hereinafter, a glass plate is used as a representative example of the inorganic substrate will be described.) When a foreign substance is sandwiched between the polymer film and the glass plate As a part of the polymer film with a foreign object as a pillar, the polymer film floats from the glass plate into a tent shape, a gap is generated between the polymer film and the glass plate, and a defect that the surface of the film becomes convex is generated. Such a defect is a blister defect (sometimes also referred to as a blister, or bubble, bulge, bubble.). When the polymer film and the inorganic substrate are bonded through a relatively thick adhesive layer, foreign matter is buried in the adhesive material layer, so it is relatively difficult to generate a blister. However, when the adhesive material layer is thin, especially when the height of the foreign material is larger than the adhesive material layer, a blister may be generated.
本案發明人等已經能夠藉由於貼合前進行高分子膜與玻璃板(無機基板)表面之清潔(洗淨)來減小泡罩。但,即使精心地進行洗淨,仍無法杜絕泡罩的產生。 [解決課題之手段]The inventors of the present case have been able to reduce the blister by cleaning (washing) the surface of the polymer film and the glass plate (inorganic substrate) before lamination. However, even if the washing is performed carefully, the generation of blister cannot be prevented. [Means for solving problems]
本案發明人等為了解決前述課題而努力研究的結果,發現了一種處方,即使在高分子膜與由無機物構成之支持體的疊層體中黏接層較薄的情形,或黏接層實質上不存在的情形,亦可抑制泡罩的產生,並可實現高製造產率,而完成了本發明。As a result of intensive research in order to solve the aforementioned problems, the inventors of the present case have found a prescription, even when the adhesive layer is thin in a laminate of a polymer film and a support made of an inorganic substance, or the adhesive layer is substantially In the absence of such a situation, the generation of blister can be suppressed, and a high manufacturing yield can be achieved, and the present invention has been completed.
亦即本發明具有下列構成。 [1]一種聚醯亞胺膜及無機基板之疊層體,其特徵為:在聚醯亞胺膜及無機基板之疊層體中,至少滿足(a)或(b)之條件; (a)泡罩缺點之個數密度為50個/平方米以下,泡罩之平均高度為2μm以下,泡罩個數密度(個/平方米)與泡罩之平均高度(μm)的乘積為20以下; (b)聚醯亞胺膜及無機基板之疊層體中,高度3μm以上之泡罩個數為10個/平方米以下。 [2]如[1]之聚醯亞胺膜及無機基板之疊層體,其面積為0.157平方米以上。 [3]如[1]或[2]之聚醯亞胺膜及無機基板之疊層體,其中,該泡罩之內部內包有碳化物粒子。 [4]如[1]至[3]中任一項之聚醯亞胺膜及無機基板之疊層體,其中,在該聚醯亞胺膜與無機基板之間存在厚度5nm~500nm之矽烷偶聯劑縮合物層。 [5]一種如[1]至[4]中任一項之聚醯亞胺膜及無機基板之疊層體之製造方法,其特徵為:將聚醯亞胺膜與無機基板製成疊層體後,於350℃以上未達600℃之溫度進行熱處理。 [6]如[5]之聚醯亞胺膜及無機基板之疊層體之製造方法,係將聚醯亞胺膜與無機基板製成疊層體後,於350℃以上未達600℃之溫度進行熱處理,並在熱處理後以10℃/分鐘以上、90℃/分鐘以下之速度冷卻到至少200℃。 [7]如[5]或[6]之聚醯亞胺膜及無機基板之疊層體之製造方法,其中,作為將聚醯亞胺膜與無機基板疊層之前步驟,係利用預先以臭氧處理過的超純水將聚醯亞胺膜予以洗淨。That is, the present invention has the following constitutions. [1] A laminated body of a polyimide film and an inorganic substrate, characterized in that the laminated body of a polyimide film and an inorganic substrate satisfies at least the conditions (a) or (b); (a The number density of blister defects is less than 50 per square meter, the average height of the blister is less than 2 μm, and the product of the number density of blister (number / square meter) and the average height of the blister (μm) is less than 20 (B) In a laminate of a polyfluorene film and an inorganic substrate, the number of blister having a height of 3 μm or more is 10 per square meter or less. [2] The laminate of the polyimide film and the inorganic substrate according to [1], whose area is 0.157 square meters or more. [3] The laminated body of the polyimide film and the inorganic substrate according to [1] or [2], wherein the inside of the blister includes carbide particles. [4] The laminated body of a polyimide film and an inorganic substrate according to any one of [1] to [3], wherein a silane having a thickness of 5 nm to 500 nm exists between the polyimide film and the inorganic substrate. Coupling agent condensate layer. [5] A method for manufacturing a laminated body of a polyimide film and an inorganic substrate according to any one of [1] to [4], characterized in that a polyimide film and an inorganic substrate are laminated After the heat treatment, heat treatment is performed at a temperature of 350 ° C or more and less than 600 ° C. [6] The method for manufacturing a polyimide film and an inorganic substrate laminated body as described in [5], after the polyimide film and the inorganic substrate are made into a laminated body, the temperature is higher than 350 ° C and lower than 600 ° C. The heat treatment is performed at a temperature, and after the heat treatment, the temperature is cooled to at least 200 ° C at a rate of 10 ° C / minute or more and 90 ° C / minute or less. [7] The method for producing a laminated body of a polyimide film and an inorganic substrate according to [5] or [6], wherein, as a step before laminating the polyimide film and the inorganic substrate, ozone is used in advance. The treated ultrapure water cleans the polyimide membrane.
本發明中,宜進一步具有下列構成。 [8]如[6]或[7]之聚醯亞胺膜及無機基板之疊層體之製造方法,其中,在該冷卻時,係藉由使聚醯亞胺膜及無機基板之疊層體的無機基板側接觸溫度為180℃以下之金屬板而進行冷卻。 [發明之效果]In the present invention, it is preferable to further have the following constitution. [8] The method for producing a laminated body of a polyimide film and an inorganic substrate as described in [6] or [7], wherein the cooling is performed by laminating the polyimide film and the inorganic substrate The inorganic substrate side of the body is cooled by contacting a metal plate having a temperature of 180 ° C or lower. [Effect of the invention]
成為泡罩之原因的異物多種多樣。異物係存在於環境中的無機物、有機物,並藉由靜電等而附著於膜或無機基板。無機物一般能以洗淨等相對較容易地除去。附著於聚醯亞胺膜之表面的有機異物的種類中,有特徵的物質係聚醯亞胺粒子。據推定該聚醯亞胺粒子係產生於聚醯亞胺膜之製造步驟或切割步驟等。起因於該聚醯亞胺之異物,與無機物同樣可藉由洗淨而相對較容易地除去。 但,來自黏著劑、環境之有機異物、來自生物體之異物等相對較柔軟,且視情形具有黏著性,故難以利用單純的洗淨處理完全除去。另一方面,據認為如此之具有柔軟性、黏著性之有機物,相較於本發明中使用之聚醯亞胺膜及無機基板,前者之耐熱性不佳,可藉由利用高溫前處理使其發生熱分解而除去。 但,在實際的步驟中設置如此之前處理步驟並不現實,因為從加熱到冷卻會導致製造時間延長,且有新的異物附著或伴隨操作而產生傷痕等的風險高。There are many kinds of foreign materials that cause blister. A foreign substance is an inorganic substance or organic substance existing in the environment, and is attached to a film or an inorganic substrate by static electricity or the like. Inorganic substances can generally be removed relatively easily by washing or the like. Among the types of organic foreign matter adhering to the surface of the polyimide film, the characteristic substance is polyimide particles. It is presumed that the polyfluorene imine particles are generated in a manufacturing process or a cutting process of a polyfluorine film. Foreign matter caused by the polyfluorene imine can be relatively easily removed by washing in the same manner as the inorganic matter. However, since the adhesive, organic foreign matter from the environment, and foreign matter from the living body are relatively soft, and depending on the situation, it is difficult to completely remove it by a simple washing treatment. On the other hand, it is considered that such a flexible and adhesive organic substance has a lower heat resistance than a polyimide film and an inorganic substrate used in the present invention, and can be made by using a high-temperature pretreatment. It is removed by thermal decomposition. However, it is not realistic to set such a previous processing step in the actual step, because heating to cooling will lead to a prolonged manufacturing time, and there is a high risk of new foreign matter adhering or scarring due to operation.
本發明之特徵為:藉由將膜與無機基板予以貼合後以預定之條件進行熱處理,即使是膜與無機基板之間存在有機物異物的情況,亦可減低泡罩之高度,改善成實用上沒有問題之水平。亦即,本發明之效果在於:即使是內部有異物之泡罩,內部之異物為碳化物時,泡罩之高度仍低,可將產能的降低壓抑為最低限,又,可將具有成為問題之高度的有機異物內包泡罩利用特定之處理方法變換成碳化物異物內包泡罩,而將泡罩之高度減低至沒有問題之水平。The present invention is characterized in that by bonding the film to the inorganic substrate and performing heat treatment under predetermined conditions, the height of the blister can be reduced even if there is an organic foreign matter between the film and the inorganic substrate, and it can be improved in practical use. No problem level. That is, the effect of the present invention is that even if the blister has a foreign substance inside, when the foreign substance inside is a carbide, the height of the blister is still low, which can suppress the reduction of the production capacity to the minimum, and it can also become a problem. The height of the organic foreign body inner blister is transformed into a carbide foreign body inner blister by a specific processing method, and the height of the blister is reduced to a level without problems.
本發明中,特別是可藉由將熱處理後之冷卻速度控制為預定範圍內,而使本發明之效果更為顯著。亦即,藉由以特定速度進行冷卻,可使因有機物之分解氣體而膨脹了的泡罩快速地收縮。冷卻速度長到超過必要時,在泡罩充分收縮之前,已於高溫降低了的聚醯亞胺膜之彈性模量恢復至原來的值,聚醯亞胺膜本身的形狀保持性提高,故有時會有無法充分減低泡罩之高度的情況。 大尺寸之基板容易產生加熱速度、冷卻速度不均。本發明中,減小冷卻速度的不均尤其重要。故,本發明中,冷卻時宜藉由使疊層體直接接觸高比熱之物質,例如直接接觸金屬板等而進行冷卻。In the present invention, in particular, the effect of the present invention can be made more significant by controlling the cooling rate after the heat treatment within a predetermined range. That is, by cooling at a specific speed, the blister that has been expanded by the decomposition gas of organic matter can be rapidly contracted. When the cooling rate is longer than necessary, the elastic modulus of the polyimide film, which has been reduced at a high temperature, is restored to the original value before the blister is fully contracted, and the shape retention of the polyimide film itself is improved. In some cases, the height of the blister cannot be sufficiently reduced. Large substrates are prone to uneven heating and cooling rates. In the present invention, it is particularly important to reduce unevenness in the cooling rate. Therefore, in the present invention, it is desirable to cool the laminate by directly contacting the laminate with a substance having a high specific heat, for example, directly contacting a metal plate or the like during cooling.
又,本發明中就尤佳態樣而言,可藉由以預先進行過臭氧處理之超純水將疊層前之聚醯亞胺膜予以洗淨,而獲得充分的效果。亦即,泡罩之原因係由有機異物產生之分解氣體。藉由已預先利用臭氧處理使有機物分解除去了的超純水將聚醯亞胺表面予以洗淨,將原本附著的有機異物洗淨除去,同時洗淨液本身所含之有機異物亦因臭氧處理而發生分解並低分子化,故固體物之再附著受到抑制,就結果而言可大幅減低異物密度。 就臭氧處理而言,例如可藉由使洗淨水曝露於利用臭氧產生器(ozonizer)等生成的含臭氧之潔淨空氣而進行。本發明中,洗淨水中之臭氧濃度宜為3ppm以上,較佳為6ppm以上,更佳為9ppm以上,尤佳為20ppm以上。臭氧濃度的上限並無特別限制,為大約200ppm。In addition, in a particularly preferred aspect of the present invention, a sufficient effect can be obtained by cleaning the polyimide film before lamination with ultrapure water that has been treated with ozone in advance. That is, the cause of the blister is a decomposed gas generated by an organic foreign substance. The surface of the polyimide is washed with ultra-pure water that has been decomposed and removed by using ozone treatment in advance, and the originally attached organic foreign matter is washed away. At the same time, the organic foreign matter contained in the cleaning solution itself is also treated with ozone. Decomposition occurs and the molecular weight is reduced, so that the re-adhesion of solid matter is suppressed, and as a result, the density of foreign matter can be greatly reduced. The ozone treatment can be performed, for example, by exposing the washing water to ozone-containing clean air generated by an ozone generator or the like. In the present invention, the ozone concentration in the washing water is preferably 3 ppm or more, preferably 6 ppm or more, more preferably 9 ppm or more, and even more preferably 20 ppm or more. The upper limit of the ozone concentration is not particularly limited and is about 200 ppm.
本發明之疊層體中,係使用無機基板作為支持基板。無機基板係由無機物構成之板狀物,例如可例示玻璃板、陶瓷板、半導體晶圓、金屬板等。又,亦可使用選自於玻璃板、陶瓷板、半導體晶圓、金屬板中之2種以上疊層而得的複合基板。進一步,可例示選自於玻璃、陶瓷、金屬中之一種以上之材料以粉體形態分散於其他無機材料中或有機材料中而成的複合體。進一步,可例示具有選自於玻璃、陶瓷、金屬中之一種以上之纖維狀物在其他無機材料中、或有機材料中複合化而得之纖維強化複合結構的基板材料等。In the laminated body of the present invention, an inorganic substrate is used as a supporting substrate. The inorganic substrate is a plate made of an inorganic substance, and examples thereof include glass plates, ceramic plates, semiconductor wafers, and metal plates. Further, a composite substrate obtained by laminating two or more kinds selected from a glass plate, a ceramic plate, a semiconductor wafer, and a metal plate may be used. Furthermore, a composite body in which one or more materials selected from glass, ceramics, and metals are dispersed in powder form in other inorganic materials or organic materials can be exemplified. Further, a substrate material having a fiber-reinforced composite structure in which a fibrous material selected from glass, ceramic, and metal is compounded in other inorganic materials or organic materials can be exemplified.
係本發明中之無機基板的玻璃板及含有玻璃之基板材料所使用的玻璃,可例示:石英玻璃、高矽酸玻璃(96%二氧化矽)、蘇打石灰玻璃、鉛玻璃、鋁硼矽酸玻璃、硼矽酸玻璃(Pyrex(註冊商標))、硼矽酸玻璃(無鹼)、硼矽酸玻璃(微小片)、鋁矽酸鹽玻璃等。本發明中,該等之中線膨脹係數為5ppm/K以下者尤其理想,若為市售品,則宜使用係液晶顯示元件用玻璃之康寧公司製的「Corning(註冊商標)7059」、「Corning(註冊商標)1737」、「EAGLE XG」、旭硝子公司製的「AN100」、日本電氣硝子公司製的「OA10G」、SCHOTT公司製的「AF32」等較理想。The glass plate of the inorganic substrate and the glass-containing substrate material in the present invention can be exemplified by quartz glass, high silica glass (96% silicon dioxide), soda lime glass, lead glass, aluminum borosilicate Glass, borosilicate glass (Pyrex (registered trademark)), borosilicate glass (alkali-free), borosilicate glass (microchip), aluminosilicate glass, etc. In the present invention, those having a median expansion coefficient of 5 ppm / K or less are particularly preferable. If they are commercially available products, "Corning (registered trademark) 7059" and "Corning (registered trademark) 7059", which are made of glass for liquid crystal display elements, should be used. "Corning (registered trademark) 1737", "EAGLE XG", "AN100" manufactured by Asahi Glass Company, "OA10G" manufactured by Japan Electric Glass Company, "AF32" manufactured by SCHOTT, etc. are preferable.
係本發明中之無機基板的陶瓷板,可例示由選自於下列中之一種以上之材料構成的陶瓷板:氧化鋁、莫來石、氮化鋁、碳化矽、氮化矽、氮化硼、結晶化玻璃、堇青石(cordierite)、鋰輝石、Pb-BSG+CaZrO3 +Al2 O3 、結晶化玻璃+Al2 O3 、結晶化Ca-硼矽酸玻璃、硼矽酸玻璃+石英、硼矽酸玻璃+Al2 O3 、Pb+硼矽酸玻璃+Al2 O3 、玻璃陶瓷、微晶玻璃(zerodur)材等基板用陶瓷;氧化鈦、鈦酸鍶、鈦酸鈣、鈦酸鎂、氧化鋁、氧化鎂、塊滑石(steatite)、BaTi4 O9 、BaTi4 O9 +CaZrO3 、BaSrCaZrTiO3 、Ba(TiZr)O3 、PMN-PT、PFN-PFW等電容器材料;PbNb2 O6 、Pb0.5 Be0.5 Nb2 O6 、PbTiO3 、BaTiO3 、PZT、0.855PZT-95PT-0.5BT、0.873PZT-0.97PT-0.3BT、PLZT等壓電材料等。The ceramic plate of the inorganic substrate in the present invention can be exemplified by a ceramic plate made of one or more materials selected from the group consisting of alumina, mullite, aluminum nitride, silicon carbide, silicon nitride, and boron nitride. , Crystallized glass, cordierite, hectorite, Pb-BSG + CaZrO 3 + Al 2 O 3 , crystallized glass + Al 2 O 3 , crystallized Ca-borosilicate glass, borosilicate glass + quartz, Ceramics for substrates such as borosilicate glass + Al 2 O 3 , Pb + borosilicate glass + Al 2 O 3 , glass ceramics, glass ceramics (zerodur) materials; titanium oxide, strontium titanate, calcium titanate, magnesium titanate, oxidation Capacitor materials such as aluminum, magnesium oxide, blockite, BaTi 4 O 9 , BaTi 4 O 9 + CaZrO 3 , BaSrCaZrTiO 3 , Ba (TiZr) O 3 , PMN-PT, PFN-PFW; PbNb 2 O 6 , Pb Piezoelectric materials such as 0.5 Be 0.5 Nb 2 O 6 , PbTiO 3 , BaTiO 3 , PZT, 0.855PZT-95PT-0.5BT, 0.873PZT-0.97PT-0.3BT, PLZT, etc.
作為構成本發明中之金屬板的金屬材料,包括如W、Mo、Pt、Fe、Ni、Au之單一元素金屬;如鎳鉻合金(Inconel)、蒙乃爾合金(Monel)、鎳蒙合金(Nimonic)、碳銅、Fe-Ni系恆範鋼合金、超級恆範鋼合金之合金等。又,亦包括於該等金屬附加其他金屬層、陶瓷層而成的多層金屬板。此時,若與附加層之全體的CTE低的話,則主金屬層也可使用Cu、Al等。作為附加金屬層使用之金屬,只要是具有與聚醯亞胺膜之密接性牢固、不會擴散、耐藥品性、耐熱性良好等特性者即可,並無限定,可列舉鉻、鎳、TiN、含Mo之Cu等作為理想例。As the metal material constituting the metal plate in the present invention, it includes single element metals such as W, Mo, Pt, Fe, Ni, and Au; such as nickel-chromium alloy (Inconel), Monel, Nimonic (Nimonic ), Carbon copper, Fe-Ni based Hengfan steel alloy, super Hengfan steel alloy and so on. It also includes multilayer metal plates made by adding other metal layers and ceramic layers to these metals. In this case, if the CTE with the entire additional layer is low, Cu, Al, or the like may be used as the main metal layer. The metal used as the additional metal layer is not limited as long as it has characteristics such as strong adhesion to the polyimide film, non-diffusion, good chemical resistance, and heat resistance. Examples include chromium, nickel, and TiN. , Cu containing Mo, and the like are ideal examples.
本發明中之半導體晶圓,可使用矽晶圓、碳化矽晶圓、化合物半導體晶圓等,矽晶圓係於薄板上加工單晶或多晶矽而得,摻雜成n型或p型之矽晶圓、純質矽晶圓等全包括,又,也包括在矽晶圓之表面沉積氧化矽層、各種薄膜的矽晶圓,除矽晶圓以外,也可使用鍺、矽-鍺、鎵-砷、鋁-鎵-銦、氮-磷-砷-銻、SiC、InP(磷化銦)、InGaAs、GaInNAs、LT、LN、ZnO(氧化鋅)、CdTe(碲化鎘)、ZnSe(硒化鋅)等半導體晶圓、化合物半導體晶圓等。The semiconductor wafer in the present invention may be a silicon wafer, a silicon carbide wafer, a compound semiconductor wafer, etc. The silicon wafer is obtained by processing single-crystal or polycrystalline silicon on a thin plate, and is doped into n-type or p-type silicon. Including wafers, pure silicon wafers, etc., and also silicon wafers that deposit silicon oxide layers and various films on the surface of silicon wafers. In addition to silicon wafers, germanium, silicon-germanium, and gallium can also be used. -Arsenic, aluminum-gallium-indium, nitrogen-phosphorus-arsenic-antimony, SiC, InP (indium phosphide), InGaAs, GaInNAs, LT, LN, ZnO (zinc oxide), CdTe (cadmium telluride), ZnSe (selenium Semiconductor wafers such as zinc) and compound semiconductor wafers.
本發明中之無機基板之面積宜為0.157平方米以上。更具體而言,長邊為45cm以上,短邊為35cm以上之長方形較佳。The area of the inorganic substrate in the present invention is preferably 0.157 square meters or more. More specifically, a rectangle having a long side of 45 cm or more and a short side of 35 cm or more is preferable.
可對於該等成為支持體之無機基板實施UV臭氧處理、真空電漿處理、大氣壓電漿處理、電暈處理、火燄處理、ITRO處理、UV臭氧處理、曝露於活性氣體之處理等活化處理。該等處理主要具有將無機基板表面之有機物等附著污染物除去的清潔效果、及使無機基板表面活性化並改善與聚醯亞胺膜之黏接性的效果。Such inorganic substrates as a support may be subjected to activation treatments such as UV ozone treatment, vacuum plasma treatment, atmospheric piezoelectric plasma treatment, corona treatment, flame treatment, ITRO treatment, UV ozone treatment, and treatment exposed to active gas. These treatments mainly have a cleaning effect of removing organic pollutants and other attached pollutants on the surface of the inorganic substrate, and an effect of activating the surface of the inorganic substrate and improving the adhesion to the polyimide film.
本發明中之聚醯亞胺係藉由醯亞胺鍵形成之多聚體。一般而言,聚醯亞胺係以四羧酸二酐與二胺之縮合物的形式獲得。通常的聚醯亞胺之製法,已知有如下方法:將使四羧酸二酐與二胺在溶劑中反應而獲得之聚醯胺酸(聚醯亞胺前驅體)溶液塗布於支持體,並進行乾燥而製成前驅體膜,進一步,藉由加熱或觸媒的作用使醯亞胺化反應發生而轉化成聚醯亞胺。於使聚醯亞胺膜化時將前驅體膜從支持體剝離並進行醯亞胺化的方法係習知。又,於將支持體予以被覆之用途,不剝離而進行醯亞胺化的方法亦係習知。在將聚醯亞胺膜作為可撓性器件之基板使用的用途中,正研究使將前驅體溶液塗布於支持體上並乾燥,在支持體上進行醯亞胺化的方法實用化。The polyfluorene imide in the present invention is a polymer formed by a hydrazone bond. Generally speaking, polyimide is obtained as a condensation product of tetracarboxylic dianhydride and diamine. A general method for producing polyimide is known as follows: a polyamic acid (polyimide precursor) solution obtained by reacting a tetracarboxylic dianhydride and a diamine in a solvent is applied to a support, The precursor film is dried and further converted into polyfluorene imine by the reaction of fluorene imine by heating or the action of a catalyst. When the polyfluorene imide is formed into a film, a method of peeling the precursor film from the support and performing the imidization is known. In addition, for the application of coating a support, a method of performing imidization without peeling is also known. In applications where a polyimide film is used as a substrate for a flexible device, research is being conducted to put a precursor solution onto a support and dry it, and a method for performing imidization on the support is being put into practical use.
就本發明中之四羧酸二酐而言,較佳為可使用芳香族四羧酸二酐、脂環族四羧酸二酐。考量耐熱性的觀點,宜為芳香族四羧酸二酐,考量光透射性的觀點,宜為脂環族四羧酸二酐。四羧酸二酐可單獨使用,亦可將二種以上倂用。The tetracarboxylic dianhydride in the present invention is preferably an aromatic tetracarboxylic dianhydride or an alicyclic tetracarboxylic dianhydride. From the viewpoint of heat resistance, an aromatic tetracarboxylic dianhydride is preferred, and from the viewpoint of light transmittance, an alicyclic tetracarboxylic dianhydride is preferred. Tetracarboxylic dianhydride can be used alone or in combination of two or more kinds.
本發明中之芳香族四羧酸,可列舉:均苯四甲酸二酐、3,3’,4,4’-聯苯四羧酸二酐、4,4’-氧基二苯二甲酸二酐、3,3’,4,4’-二苯甲酮四羧酸二酐、3,3’,4,4’-二苯碸四羧酸二酐、2,2-雙[4-(3,4-二羧基苯氧基)苯基]丙酸酐等。本發明中,宜使用均苯四甲酸二酐。Examples of the aromatic tetracarboxylic acid in the present invention include pyromellitic dianhydride, 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride, and 4,4'-oxydiphthalic acid dianhydride. Anhydride, 3,3 ', 4,4'-benzophenonetetracarboxylic dianhydride, 3,3', 4,4'-diphenylfluorenetetracarboxylic dianhydride, 2,2-bis [4- ( 3,4-dicarboxyphenoxy) phenyl] propionic anhydride and the like. In the present invention, pyromellitic dianhydride is preferably used.
本發明中之脂環族四羧酸類,例如可列舉:環丁烷四羧酸、1,2,4,5-環己烷四羧酸、3,3’,4,4’-雙環己基四羧酸等脂環族四羧酸、及它們的酸酐。該等之中,宜為具有2個酸酐結構之二酐(例如,環丁烷四羧酸二酐、1,2,4,5-環己烷四羧酸二酐、3,3’,4,4’-雙環己基四羧酸二酐等)。此外,脂環族四羧酸類可單獨使用,亦可將二種以上倂用。 就脂環族四羧酸類而言,重視透明性的情況下,例如宜為全部四羧酸類之80質量%以上,更佳為90質量%以上,尤佳為95質量%以上。Examples of the alicyclic tetracarboxylic acids in the present invention include cyclobutane tetracarboxylic acid, 1,2,4,5-cyclohexanetetracarboxylic acid, 3,3 ', 4,4'-dicyclohexyl tetracarboxylic acid. Alicyclic tetracarboxylic acids such as carboxylic acids, and their anhydrides. Among these, a dianhydride having two anhydride structures (for example, cyclobutanetetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, 3,3 ', 4 , 4'-Bicyclohexyltetracarboxylic dianhydride, etc.). The alicyclic tetracarboxylic acids may be used alone or in combination of two or more kinds. In the case of alicyclic tetracarboxylic acids, when transparency is important, for example, it is preferably 80% by mass or more of all tetracarboxylic acids, more preferably 90% by mass or more, and even more preferably 95% by mass or more.
本發明中之二胺類並無特別限制,可使用通常用於聚醯亞胺合成的芳香族二胺類、脂肪族二胺類、脂環族二胺類等。考量耐熱性的觀點,宜為芳香族二胺類,芳香族二胺類之中,可使用具有苯并唑結構之芳香族二胺類。使用具有苯并唑結構之芳香族二胺類的話,可展現高耐熱性,同時可展現高彈性模量、低熱收縮性、低線膨脹係數。二胺類可單獨使用,亦可將二種以上倂用。The diamines in the present invention are not particularly limited, and aromatic diamines, aliphatic diamines, alicyclic diamines, and the like that are generally used in the synthesis of polyimide can be used. From the viewpoint of heat resistance, aromatic diamines are preferred. Among aromatic diamines, benzo Aromatic diamines of the azole structure. Use with benzo The aromatic diamines of the azole structure can exhibit high heat resistance, high elastic modulus, low thermal shrinkage, and low linear expansion coefficient. Diamines can be used alone or in combination of two or more.
本發明之二胺類中,就芳香族二胺類而言,例如可列舉:2,2’-二甲基-4,4’-二胺基聯苯、1,4-雙[2-(4-胺基苯基)-2-丙基]苯(雙苯胺)、1,4-雙(4-胺基-2-三氟甲基苯氧基)苯、2,2’-二(三氟甲基)-4,4’-二胺基聯苯、4,4’-雙(4-胺基苯氧基)聯苯、4,4’-雙(3-胺基苯氧基)聯苯、雙[4-(3-胺基苯氧基)苯基]酮、雙[4-(3-胺基苯氧基)苯基]硫醚、雙[4-(3-胺基苯氧基)苯基]碸、2,2-雙[4-(3-胺基苯氧基)苯基]丙烷、2,2-雙[4-(3-胺基苯氧基)苯基]-1,1,1,3,3,3-六氟丙烷、間苯二胺、鄰苯二胺、對苯二胺、間胺基苄胺、對胺基苄胺、3,3’-二胺基二苯醚、3,4’-二胺基二苯醚、4,4’-二胺基二苯醚、3,3’-二胺基二苯基硫醚、3,3’-二胺基二苯基亞碸、3,4’-二胺基二苯基亞碸、4,4’-二胺基二苯基亞碸、3,3’-二胺基二苯碸、3,4’-二胺基二苯碸、4,4’-二胺基二苯碸、3,3’-二胺基二苯甲酮、3,4’-二胺基二苯甲酮、4,4’-二胺基二苯甲酮、3,3’-二胺基二苯基甲烷、3,4’-二胺基二苯基甲烷、4,4’-二胺基二苯基甲烷、雙[4-(4-胺基苯氧基)苯基]甲烷、1,1-雙[4-(4-胺基苯氧基)苯基]乙烷、1,2-雙[4-(4-胺基苯氧基)苯基]乙烷、1,1-雙[4-(4-胺基苯氧基)苯基]丙烷、1,2-雙[4-(4-胺基苯氧基)苯基]丙烷、1,3-雙[4-(4-胺基苯氧基)苯基]丙烷、2,2-雙[4-(4-胺基苯氧基)苯基]丙烷、1,1-雙[4-(4-胺基苯氧基)苯基]丁烷、1,3-雙[4-(4-胺基苯氧基)苯基]丁烷、1,4-雙[4-(4-胺基苯氧基)苯基]丁烷、2,2-雙[4-(4-胺基苯氧基)苯基]丁烷、2,3-雙[4-(4-胺基苯氧基)苯基]丁烷、2-[4-(4-胺基苯氧基)苯基]-2-[4-(4-胺基苯氧基)-3-甲基苯基]丙烷、2,2-雙[4-(4-胺基苯氧基)-3-甲基苯基]丙烷、2-[4-(4-胺基苯氧基)苯基]-2-[4-(4-胺基苯氧基)-3,5-二甲基苯基]丙烷、2,2-雙[4-(4-胺基苯氧基)-3,5-二甲基苯基]丙烷、2,2-雙[4-(4-胺基苯氧基)苯基]-1,1,1,3,3,3-六氟丙烷、1,4-雙(3-胺基苯氧基)苯、1,3-雙(3-胺基苯氧基)苯、1,4-雙(4-胺基苯氧基)苯、4,4’-雙(4-胺基苯氧基)聯苯、雙[4-(4-胺基苯氧基)苯基]酮、雙[4-(4-胺基苯氧基)苯基]硫醚、雙[4-(4-胺基苯氧基)苯基]亞碸、雙[4-(4-胺基苯氧基)苯基]碸、雙[4-(3-胺基苯氧基)苯基]醚、雙[4-(4-胺基苯氧基)苯基]醚、1,3-雙[4-(4-胺基苯氧基)苯甲醯基]苯、1,3-雙[4-(3-胺基苯氧基)苯甲醯基]苯、1,4-雙[4-(3-胺基苯氧基)苯甲醯基]苯、4,4’-雙[(3-胺基苯氧基)苯甲醯基]苯、1,1-雙[4-(3-胺基苯氧基)苯基]丙烷、1,3-雙[4-(3-胺基苯氧基)苯基]丙烷、3,4’-二胺基二苯基硫醚、2,2-雙[3-(3-胺基苯氧基)苯基]-1,1,1,3,3,3-六氟丙烷、雙[4-(3-胺基苯氧基)苯基]甲烷、1,1-雙[4-(3-胺基苯氧基)苯基]乙烷、1,2-雙[4-(3-胺基苯氧基)苯基]乙烷、雙[4-(3-胺基苯氧基)苯基]亞碸、4,4’-雙[3-(4-胺基苯氧基)苯甲醯基]二苯醚、4,4’-雙[3-(3-胺基苯氧基)苯甲醯基]二苯醚、4,4’-雙[4-(4-胺基-α,α-二甲基苄基)苯氧基]二苯甲酮、4,4’-雙[4-(4-胺基-α,α-二甲基苄基)苯氧基]二苯碸、雙[4-{4-(4-胺基苯氧基)苯氧基}苯基]碸、1,4-雙[4-(4-胺基苯氧基)苯氧基-α,α-二甲基苄基]苯、1,3-雙[4-(4-胺基苯氧基)苯氧基-α,α-二甲基苄基]苯、1,3-雙[4-(4-胺基-6-三氟甲基苯氧基)-α,α-二甲基苄基]苯、1,3-雙[4-(4-胺基-6-氟苯氧基)-α,α-二甲基苄基]苯、1,3-雙[4-(4-胺基-6-甲基苯氧基)-α,α-二甲基苄基]苯、1,3-雙[4-(4-胺基-6-氰基苯氧基)-α,α-二甲基苄基]苯、3,3’-二胺基-4,4’-二苯氧基二苯甲酮、4,4’-二胺基-5,5’-苯氧基二苯甲酮、3,4’-二胺基-4,5’-二苯氧基二苯甲酮、3,3’-二胺基-4-苯氧基二苯甲酮、4,4’-二胺基-5-苯氧基二苯甲酮、3,4’-二胺基-4-苯氧基二苯甲酮、3,4’-二胺基-5’-苯氧基二苯甲酮、3,3’-二胺基-4,4’-二聯苯氧基二苯甲酮、4,4’-二胺基-5,5’-二聯苯氧基二苯甲酮、3,4’-二胺基-4,5’-二聯苯氧基二苯甲酮、3,3’-二胺基-4-聯苯氧基二苯甲酮、4,4’-二胺基-5-聯苯氧基二苯甲酮、3,4’-二胺基-4-聯苯氧基二苯甲酮、3,4’-二胺基-5’-聯苯氧基二苯甲酮、1,3-雙(3-胺基-4-苯氧基苯甲醯基)苯、1,4-雙(3-胺基-4-苯氧基苯甲醯基)苯、1,3-雙(4-胺基-5-苯氧基苯甲醯基)苯、1,4-雙(4-胺基-5-苯氧基苯甲醯基)苯、1,3-雙(3-胺基-4-聯苯氧基苯甲醯基)苯、1,4-雙(3-胺基-4-聯苯氧基苯甲醯基)苯、1,3-雙(4-胺基-5-聯苯氧基苯甲醯基)苯、1,4-雙(4-胺基-5-聯苯氧基苯甲醯基)苯、2,6-雙[4-(4-胺基-α,α-二甲基苄基)苯氧基]苯甲腈、及上述芳香族二胺之芳香環上之氫原子的一部分或全部取代為鹵素原子、碳數1~3之烷基或烷氧基、氰基、或烷基或烷氧基之氫原子之一部分或全部取代為鹵素原子之碳數1~3之鹵化烷基或烷氧基而得的芳香族二胺等。Among the diamines of the present invention, the aromatic diamines include, for example, 2,2'-dimethyl-4,4'-diaminobiphenyl, 1,4-bis [2- ( 4-aminophenyl) -2-propyl] benzene (bisaniline), 1,4-bis (4-amino-2-trifluoromethylphenoxy) benzene, 2,2'-bis (tris (Fluoromethyl) -4,4'-diaminobiphenyl, 4,4'-bis (4-aminophenoxy) biphenyl, 4,4'-bis (3-aminophenoxy) bi Benzene, bis [4- (3-aminophenoxy) phenyl] ketone, bis [4- (3-aminophenoxy) phenyl] sulfide, bis [4- (3-aminophenoxy Phenyl) phenyl] fluorene, 2,2-bis [4- (3-aminophenoxy) phenyl] propane, 2,2-bis [4- (3-aminophenoxy) phenyl]- 1,1,1,3,3,3-hexafluoropropane, m-phenylenediamine, o-phenylenediamine, p-phenylenediamine, m-aminobenzylamine, p-aminobenzylamine, 3,3'-diamine Diphenyl ether, 3,4'-diamino diphenyl ether, 4,4'-diamino diphenyl ether, 3,3'-diamino diphenyl sulfide, 3,3'-diamine Diphenylfluorene, 3,4'-diaminodiphenylfluorene, 4,4'-diaminodiphenylfluorene, 3,3'-diaminodiphenylfluorene, 3,4 '-Diaminodiphenylhydrazone, 4,4'-diaminodiphenylhydrazone, 3,3'-diaminobenzophenone, 3,4'-diamine Benzophenone, 4,4'-diaminobenzophenone, 3,3'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 4,4'-di Aminodiphenylmethane, bis [4- (4-aminophenoxy) phenyl] methane, 1,1-bis [4- (4-aminophenoxy) phenyl] ethane, 1, 2-bis [4- (4-aminophenoxy) phenyl] ethane, 1,1-bis [4- (4-aminophenoxy) phenyl] propane, 1,2-bis [4 -(4-aminophenoxy) phenyl] propane, 1,3-bis [4- (4-aminophenoxy) phenyl] propane, 2,2-bis [4- (4-amino Phenoxy) phenyl] propane, 1,1-bis [4- (4-aminophenoxy) phenyl] butane, 1,3-bis [4- (4-aminophenoxy) benzene Yl] butane, 1,4-bis [4- (4-aminophenoxy) phenyl] butane, 2,2-bis [4- (4-aminophenoxy) phenyl] butane , 2,3-bis [4- (4-aminophenoxy) phenyl] butane, 2- [4- (4-aminophenoxy) phenyl] -2- [4- (4- Aminophenoxy) -3-methylphenyl] propane, 2,2-bis [4- (4-aminophenoxy) -3-methylphenyl] propane, 2- [4- (4 -Aminophenoxy) phenyl] -2- [4- (4-aminophenoxy) -3,5-dimethylphenyl] propane, 2,2-bis [4- (4-amine Phenylphenoxy) -3,5-dimethylphenyl] propane, 2,2-bis [4- (4-aminophenoxy) phenyl ] -1,1,1,3,3,3-hexafluoropropane, 1,4-bis (3-aminophenoxy) benzene, 1,3-bis (3-aminophenoxy) benzene, 1,4-bis (4-aminophenoxy) benzene, 4,4'-bis (4-aminophenoxy) biphenyl, bis [4- (4-aminophenoxy) phenyl] Ketones, bis [4- (4-aminophenoxy) phenyl] sulfide, bis [4- (4-aminophenoxy) phenyl] sulfenyl, bis [4- (4-aminophenylbenzene Oxy) phenyl] fluorene, bis [4- (3-aminophenoxy) phenyl] ether, bis [4- (4-aminophenoxy) phenyl] ether, 1,3-bis [ 4- (4-aminophenoxy) benzylidene] benzene, 1,3-bis [4- (3-aminophenoxy) benzylidene] benzene, 1,4-bis [4- (3-Aminophenoxy) benzylidene] benzene, 4,4'-bis [(3-aminophenoxy) benzylidene] benzene, 1,1-bis [4- (3- Aminophenoxy) phenyl] propane, 1,3-bis [4- (3-aminophenoxy) phenyl] propane, 3,4'-diaminodiphenylsulfide, 2,2 -Bis [3- (3-aminophenoxy) phenyl] -1,1,1,3,3,3-hexafluoropropane, bis [4- (3-aminophenoxy) phenyl] Methane, 1,1-bis [4- (3-aminophenoxy) phenyl] ethane, 1,2-bis [4- (3-aminophenoxy) phenyl] ethane, bis [ 4- (3-Aminophenoxy) phenyl] fluorene, 4,4'-bis [3- (4-aminophenoxy) benzylidene] di Ether, 4,4'-bis [3- (3-aminophenoxy) benzylidene] diphenyl ether, 4,4'-bis [4- (4-amino-α, α-dimethyl Benzyl) phenoxy] benzophenone, 4,4'-bis [4- (4-amino-α, α-dimethylbenzyl) phenoxy] diphenylfluorene, bis [4- {4- (4-Aminophenoxy) phenoxy} phenyl] fluorene, 1,4-bis [4- (4-aminophenoxy) phenoxy-α, α-dimethylbenzyl Phenyl] benzene, 1,3-bis [4- (4-aminophenoxy) phenoxy-α, α-dimethylbenzyl] benzene, 1,3-bis [4- (4-amino -6-trifluoromethylphenoxy) -α, α-dimethylbenzyl] benzene, 1,3-bis [4- (4-amino-6-fluorophenoxy) -α, α- Dimethylbenzyl] benzene, 1,3-bis [4- (4-amino-6-methylphenoxy) -α, α-dimethylbenzyl] benzene, 1,3-bis [4 -(4-amino-6-cyanophenoxy) -α, α-dimethylbenzyl] benzene, 3,3'-diamino-4,4'-diphenoxybenzophenone 4,4'-diamino-5,5'-phenoxybenzophenone, 3,4'-diamino-4,5'-diphenoxybenzophenone, 3,3 ' -Diamino-4-phenoxybenzophenone, 4,4'-diamino-5-phenoxybenzophenone, 3,4'-diamino-4-phenoxydiphenyl Methanone, 3,4'-diamino-5'-phenoxybenzophenone, 3,3'-diamino-4 , 4'-Diphenoxybenzophenone, 4,4'-Diamino-5,5'-Diphenoxybenzophenone, 3,4'-Diamino-4,5 '-Diphenoxybenzophenone, 3,3'-Diamino-4-benphenoxybenzophenone, 4,4'-Diamino-5-benphenoxybenzophenone Ketone, 3,4'-diamino-4-benphenoxybenzophenone, 3,4'-diamino-5'-biphenoxybenzophenone, 1,3-bis (3 -Amino-4-phenoxybenzyl) benzene, 1,4-bis (3-amino-4-phenoxybenzyl) benzene, 1,3-bis (4-amino- 5-phenoxybenzyl) benzene, 1,4-bis (4-amino-5-phenoxybenzyl) benzene, 1,3-bis (3-amino-4-biphenyl Oxybenzyl) benzene, 1,4-bis (3-amino-4-biphenoxybenzyl) benzene, 1,3-bis (4-amino-5-biphenoxy) Benzamidine) benzene, 1,4-bis (4-amino-5-biphenoxybenzyl) benzene, 2,6-bis [4- (4-amino-α, α-di Methylbenzyl) phenoxy] benzonitrile and some or all of the hydrogen atoms on the aromatic ring of the aromatic diamine are substituted with a halogen atom, an alkyl or alkoxy group having 1 to 3 carbon atoms, and a cyano group Part or all of the hydrogen atoms of the alkyl or alkoxy group are replaced by halogen atoms Carbon atoms, a halogenated alkyl or alkoxy groups derived from aromatic diamines of 1 to 3.
本發明中之脂肪族二胺類,例如可列舉:1,2-二胺基乙烷、1,4-二胺基丁烷、1,5-二胺基戊烷、1,6-二胺基己烷、1,8-二胺基辛烷等。 本發明中之脂環族二胺類,例如可列舉:1,4-二胺基環己烷、4,4’-亞甲基雙(2,6-二甲基環己胺)等。Examples of the aliphatic diamines in the present invention include 1,2-diaminoethane, 1,4-diaminobutane, 1,5-diaminopentane, and 1,6-diamine Hexane, 1,8-diaminooctane and the like. Examples of the alicyclic diamines in the present invention include 1,4-diaminocyclohexane and 4,4'-methylenebis (2,6-dimethylcyclohexylamine).
本發明中之具有苯并唑結構之二胺類,例如可列舉:5-胺基-2-(對胺基苯基)苯并唑、6-胺基-2-(對胺基苯基)苯并唑、5-胺基-2-(間胺基苯基)苯并唑、6-胺基-2-(間胺基苯基)苯并唑、2,2’-對伸苯基雙(5-胺基苯并唑)、2,2’-對伸苯基雙(6-胺基苯并唑)、1-(5-胺基苯并唑并)-4-(6-胺基苯并唑并)苯、2,6-(4,4’-二胺基二苯基)苯并[1,2-d:5,4-d’]雙唑、2,6-(4,4’-二胺基二苯基)苯并[1,2-d:4,5-d’]雙唑、2,6-(3,4’-二胺基二苯基)苯并[1,2-d:5,4-d’]雙唑、2,6-(3,4’-二胺基二苯基)苯并[1,2-d:4,5-d’]雙唑、2,6-(3,3’-二胺基二苯基)苯并[1,2-d:5,4-d’]雙唑、2,6-(3,3’-二胺基二苯基)苯并[1,2-d:4,5-d’]雙唑等。Benzo Examples of the diamines of the azole structure include 5-amino-2- (p-aminophenyl) benzo Azole, 6-amino-2- (p-aminophenyl) benzo Azole, 5-amino-2- (m-aminophenyl) benzo Azole, 6-amino-2- (m-aminophenyl) benzo Azole, 2,2'-p-phenylene bis (5-aminobenzo Azole), 2,2'-p-phenylenebis (6-aminobenzo) Azole), 1- (5-aminobenzo Zolo) -4- (6-aminobenzo Zolo) benzene, 2,6- (4,4'-diaminodiphenyl) benzo [1,2-d: 5,4-d '] bis Azole, 2,6- (4,4'-diaminodiphenyl) benzo [1,2-d: 4,5-d '] bis Azole, 2,6- (3,4'-diaminodiphenyl) benzo [1,2-d: 5,4-d '] bis Azole, 2,6- (3,4'-diaminodiphenyl) benzo [1,2-d: 4,5-d '] bis Azole, 2,6- (3,3'-diaminodiphenyl) benzo [1,2-d: 5,4-d '] bis Azole, 2,6- (3,3'-diaminodiphenyl) benzo [1,2-d: 4,5-d '] bis Azole and so on.
本發明中,較佳使用之聚醯亞胺為由芳香族四羧酸二酐與芳香族二胺之縮合物構成的膜較理想,更佳為由選自於下列膜中之至少一種聚醯亞胺膜構成: (a)芳香族四羧酸二酐與至少包含具有苯并唑骨架之二胺的二胺之縮合物的膜、 (b)芳香族四羧酸二酐與至少包含於分子內具有醚鍵之二胺的二胺之縮合物的膜、 (c)芳香族四羧酸二酐與至少包含伸苯基二胺的二胺之縮合物的膜、 (d)聯苯四羧酸二酐與芳香族二胺之縮合物的膜。In the present invention, the polyimide preferably used is a film composed of a condensate of an aromatic tetracarboxylic dianhydride and an aromatic diamine, and more preferably at least one polyimide selected from the following films Imine film structure: (a) Aromatic tetracarboxylic dianhydride and containing at least benzo Film of a condensate of a diamine of an azole skeleton diamine, (b) A film of a condensate of an aromatic tetracarboxylic dianhydride and a diamine containing at least a diamine having an ether bond in the molecule, (c) Aromatic A film of a condensate of tetracarboxylic dianhydride and a diamine containing at least phenylenediamine, and (d) a film of a condensate of biphenyltetracarboxylic dianhydride and an aromatic diamine.
本發明中之聚醯亞胺膜之膜厚並無特別限定,宜為0.5μm~200μm,更佳為3μm~50μm。為0.5μm以下時,難以控制膜厚,可能會出現一部分聚醯亞胺缺損的部分。另一方面,為200μm以上時,有時會有製作耗費時間,難以控制膜之膜厚不均的情況。聚醯亞胺膜之膜厚不均須為5%以下,為4%以下更佳,為3%以下又更佳。The thickness of the polyimide film in the present invention is not particularly limited, but is preferably 0.5 μm to 200 μm, and more preferably 3 μm to 50 μm. When the thickness is 0.5 μm or less, it is difficult to control the film thickness, and a part of the polyfluoreneimide defect may occur. On the other hand, when it is 200 μm or more, it may take time to produce and it may be difficult to control the uneven thickness of the film. The uneven thickness of the polyimide film must be 5% or less, more preferably 4% or less, and even more preferably 3% or less.
本發明之四羧酸二酐與二胺之縮合物的膜,亦即聚醯亞胺膜可藉由溶液成膜法獲得。聚醯亞胺之溶液成膜法係如下之方法:將不銹鋼輥或無端皮帶、或PET等高分子膜作為長條或無端的支持體使用,於支持體上塗布聚醯亞胺樹脂之前驅體溶液,乾燥後從支持體剝離以製成聚醯亞胺前驅體膜,較佳為將膜之兩端以夾具或銷固持,並進行運送,同時進一步施以熱處理,使聚醯亞胺前驅體發生化學反應生成聚醯亞胺,而獲得聚醯亞胺膜。使用該方法獲得之聚醯亞胺膜,成為膜厚不均為5%以下,較佳為3.6%以下,尤佳為2.4%以下,拉伸斷裂強度為90MPa以上,較佳為180MPa以上,尤佳為350MPa以上,更佳為450MPa以上之聚醯亞胺膜。The film of the condensation product of the tetracarboxylic dianhydride and diamine of the present invention, that is, the polyfluorene imide film can be obtained by a solution film forming method. Polyimide solution film formation method is the following method: using stainless steel rolls or endless belts, or polymer films such as PET as long or endless support, coating the precursor of polyimide resin on the support After the solution is dried, it is peeled off from the support to make a polyimide precursor film. It is preferable to hold both ends of the film with a clamp or a pin and transport it, while further applying heat treatment to make the polyimide precursor. A chemical reaction occurs to form polyimide, and a polyimide film is obtained. The polyimide film obtained by this method has a non-uniform film thickness of less than 5%, preferably 3.6% or less, particularly preferably 2.4% or less, and a tensile fracture strength of 90 MPa or more, preferably 180 MPa or more, especially The polyimide film is preferably 350 MPa or more, and more preferably 450 MPa or more.
本發明中,為了調整聚醯亞胺膜之性狀,可於聚醯亞胺中含有無機物,但需保持在必要之最低限度。一般使高分子膜化時,添加少量的稱為潤滑劑之無機粒子,使膜表面積極地產生微小的凸部,將膜與膜或膜與平滑面重疊時,在其間夾入空氣層,藉此展現膜的光滑性。本發明中,聚醯亞胺膜中所含之氧化矽成分宜保持在6000ppm以下,較佳為4500ppm以下,更較佳為1800ppm以下,尤佳為900ppm以下。添加過剩的潤滑劑時,膜表面之粗糙度變大,有時會有妨礙第2聚醯亞胺膜之剝離性的情況。In the present invention, in order to adjust the properties of the polyimide film, an inorganic substance may be contained in the polyimide, but it is necessary to keep it to the minimum necessary. Generally, when a polymer film is formed, a small amount of inorganic particles called lubricants are added to actively generate tiny convex portions on the surface of the film. When the film and the film or the film and the smooth surface are overlapped, an air layer is sandwiched therebetween. This exhibits the smoothness of the film. In the present invention, the silicon oxide component contained in the polyfluorene imide film should preferably be kept below 6000 ppm, preferably below 4500 ppm, more preferably below 1800 ppm, even more preferably below 900 ppm. When an excessive amount of lubricant is added, the roughness of the film surface may increase, and the peelability of the second polyimide film may be hindered in some cases.
本發明中,係支持體之無機基板與聚醯亞胺膜的黏接方式,可使用聚矽氧樹脂、環氧樹脂、丙烯酸樹脂、聚酯樹脂等公知的黏接劑、黏著劑。但,本發明中較佳之黏接方式,係利用膜厚為5μm以下之極薄黏接、黏著層所為之黏接方式,或較佳為實質上不使用黏接劑、黏著劑之黏接方式。In the present invention, as the method of bonding the inorganic substrate of the support to the polyimide film, known adhesives and adhesives such as silicone resin, epoxy resin, acrylic resin, and polyester resin can be used. However, the preferred adhesive method in the present invention is an adhesive method using an extremely thin adhesive or adhesive layer having a film thickness of 5 μm or less, or an adhesive method that does not substantially use an adhesive or an adhesive. .
本發明中之聚醯亞胺膜及無機基板之疊層體的面積宜為0.157平方米以上。此外,就聚醯亞胺膜及無機基板之疊層體的面積而言,當聚醯亞胺膜與無機基板之尺寸不同時,係指兩者重疊之部分的面積。聚醯亞胺膜及無機基板之疊層體的面積較佳為0.25平方米以上,尤佳為0.46平方米以上,更佳為0.62平方米以上,又尤佳為0.98平方米以上。The area of the laminated body of the polyimide film and the inorganic substrate in the present invention is preferably 0.157 square meters or more. In addition, in terms of the area of the laminate of the polyimide film and the inorganic substrate, when the sizes of the polyimide film and the inorganic substrate are different, it means the area of the portion where the two overlap. The area of the laminate of the polyimide film and the inorganic substrate is preferably 0.25 square meters or more, particularly preferably 0.46 square meters or more, more preferably 0.62 square meters or more, and even more preferably 0.98 square meters or more.
本發明中,就實質上不使用黏接劑、黏著劑之黏接方式而言,可使用利用矽烷偶聯劑進行黏接的方法。亦即,本發明中,宜於無機基板與聚醯亞胺膜之間具有矽烷偶聯劑層。 本發明中之矽烷偶聯劑,係指物理性或化學性地介隔在無機基板與聚醯亞胺膜之間,並具有使兩者間之黏接力提高之作用的化合物。 作為矽烷偶聯劑之較佳具體例,可列舉:N-2-(胺基乙基)-3-胺基丙基甲基二甲氧基矽烷、N-2-(胺基乙基)-3-胺基丙基三甲氧基矽烷、N-2-(胺基乙基)-3-胺基丙基三乙氧基矽烷、3-胺基丙基三甲氧基矽烷、3-胺基丙基三乙氧基矽烷、3-三乙氧基矽基-N-(1,3-二甲基-亞丁基)丙胺、2-(3,4-環氧環己基)乙基三甲氧基矽烷、3-環氧丙氧基丙基三甲氧基矽烷、3-環氧丙氧基丙基甲基二乙氧基矽烷、3-環氧丙氧基丙基三乙氧基矽烷、乙烯基三氯矽烷、乙烯基三甲氧基矽烷、乙烯基三乙氧基矽烷、2-(3,4-環氧環己基)乙基三甲氧基矽烷、3-環氧丙氧基丙基三甲氧基矽烷、3-環氧丙氧基丙基甲基二乙氧基矽烷、3-環氧丙氧基丙基三乙氧基矽烷、對苯乙烯基三甲氧基矽烷、3-甲基丙烯醯氧丙基甲基二甲氧基矽烷、3-甲基丙烯醯氧丙基三甲氧基矽烷、3-甲基丙烯醯氧丙基甲基二乙氧基矽烷、3-甲基丙烯醯氧丙基三乙氧基矽烷、3-丙烯醯氧丙基三甲氧基矽烷、N-苯基-3-胺基丙基三甲氧基矽烷、N-(乙烯基苄基)-2-胺基乙基-3-胺基丙基三甲氧基矽烷鹽酸鹽、3-脲基丙基三乙氧基矽烷、3-氯丙基三甲氧基矽烷、3-巰基丙基甲基二甲氧基矽烷、3-巰基丙基三甲氧基矽烷、雙(三乙氧基矽基丙基)四硫醚、3-異氰酸酯丙基三乙氧基矽烷、參-(3-三甲氧基矽基丙基)異氰尿酸酯、氯甲基苯乙基三甲氧基矽烷、氯甲基三甲氧基矽烷、胺基苯基三甲氧基矽烷、胺基苯乙基三甲氧基矽烷、胺基苯基胺基甲基苯乙基三甲氧基矽烷、六甲基二矽氮烷等。In the present invention, in a bonding method that does not substantially use an adhesive or an adhesive, a method using a silane coupling agent for bonding can be used. That is, in the present invention, it is preferable to have a silane coupling agent layer between the inorganic substrate and the polyimide film. The silane coupling agent in the present invention refers to a compound that is physically or chemically interposed between an inorganic substrate and a polyimide film and has an effect of improving the adhesion between the two. Preferred specific examples of the silane coupling agent include N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, and N-2- (aminoethyl)- 3-aminopropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyl Triethoxysilane, 3-triethoxysilyl-N- (1,3-dimethyl-butylene) propylamine, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane , 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, vinyltris Chlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane , 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropane Methyl methyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3- Methacryloxypropyltriethoxysilane, 3-propenyloxypropyltrimethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N- (vinylbenzyl)- 2-aminoethyl-3-aminopropyltrimethoxysilane hydrochloride, 3-ureidopropyltriethoxysilane, 3-chloropropyltrimethoxysilane, 3-mercaptopropylmethyl Dimethoxysilane, 3-mercaptopropyltrimethoxysilane, bis (triethoxysilylpropyl) tetrasulfide, 3-isocyanatepropyltriethoxysilane, gins- (3-trimethoxy (Silylpropyl) isocyanurate, chloromethylphenethyltrimethoxysilane, chloromethyltrimethoxysilane, aminophenyltrimethoxysilane, aminophenylethyltrimethoxysilane, amine Phenylphenylaminomethylphenethyltrimethoxysilane, hexamethyldisilazane and the like.
本發明中可使用之矽烷偶聯劑,除上述外,亦可使用:正丙基三甲氧基矽烷、丁基三氯矽烷、2-氰基乙基三乙氧基矽烷、環己基三氯矽烷、癸基三氯矽烷、二乙醯氧基二甲基矽烷、二乙氧基二甲基矽烷、二甲氧基二甲基矽烷、二甲氧基二苯基矽烷、二甲氧基甲基苯基矽烷、十二烷基三氯矽烷、十二烷基三甲氧基矽烷、乙基三氯矽烷、己基三甲氧基矽烷、十八烷基三乙氧基矽烷、十八烷基三甲氧基矽烷、正辛基三氯矽烷、正辛基三乙氧基矽烷、正辛基三甲氧基矽烷、三乙氧基乙基矽烷、三乙氧基甲基矽烷、三甲氧基甲基矽烷、三甲氧基苯基矽烷、戊基三乙氧基矽烷、戊基三氯矽烷、三乙醯氧基甲基矽烷、三氯己基矽烷、三氯甲基矽烷、三氯十八烷基矽烷、三氯丙基矽烷、三氯十四烷基矽烷、三甲氧基丙基矽烷、烯丙基三氯矽烷、烯丙基三乙氧基矽烷、烯丙基三甲氧基矽烷、二乙氧基甲基乙烯基矽烷、二甲氧基甲基乙烯基矽烷、三氯乙烯基矽烷、三乙氧基乙烯基矽烷、乙烯基參(2-甲氧基乙氧基)矽烷、三氯-2-氰基乙基矽烷、二乙氧基(3-環氧丙氧基丙基)甲基矽烷、3-環氧丙氧基丙基(二甲氧基)甲基矽烷、3-環氧丙氧基丙基三甲氧基矽烷等。In addition to the above-mentioned silane coupling agents which can be used in the present invention, n-propyltrimethoxysilane, butyltrichlorosilane, 2-cyanoethyltriethoxysilane, cyclohexyltrichlorosilane , Decyltrichlorosilane, diethoxymethoxydimethylsilane, diethoxydimethylsilane, dimethoxydimethylsilane, dimethoxydiphenylsilane, dimethoxymethyl Phenylsilane, dodecyltrichlorosilane, dodecyltrimethoxysilane, ethyltrichlorosilane, hexyltrimethoxysilane, octadecyltriethoxysilane, octadecyltrimethoxy Silane, n-octyltrichlorosilane, n-octyltriethoxysilane, n-octyltrimethoxysilane, triethoxyethylsilane, triethoxymethylsilane, trimethoxymethylsilane, trimethylsilane Oxyphenylsilane, pentyltriethoxysilane, pentyltrichlorosilane, triethoxymethylsilane, trichlorohexylsilane, trichloromethylsilane, trichlorooctadecylsilane, trichloro Propylsilane, trichlorotetradecylsilane, trimethoxypropylsilane, allyltrichlorosilane, allyltriethoxysilane Allyltrimethoxysilane, diethoxymethylvinylsilane, dimethoxymethylvinylsilane, trichlorovinylsilane, triethoxyvinylsilane, vinyl ginseng (2-methoxy Ethoxy) silane, trichloro-2-cyanoethylsilane, diethoxy (3-glycidoxypropyl) methylsilane, 3-glycidoxypropyl (dimethoxy) Group) methylsilane, 3-glycidoxypropyltrimethoxysilane, and the like.
又,矽烷偶聯劑中亦可適當加入其他烷氧基矽烷類,例如可加入四甲氧基矽烷、四乙氧基矽烷等。又,於矽烷偶聯劑中適當加入其他烷氧基矽烷類,例如加入四甲氧基矽烷、四乙氧基矽烷等的情況,亦包括不添加的情況,可在進行混合、加熱操作,並在略微進行反應後再使用。Further, other alkoxysilanes may be appropriately added to the silane coupling agent, for example, tetramethoxysilane, tetraethoxysilane, and the like may be added. In addition, other alkoxysilanes are appropriately added to the silane coupling agent, for example, the case of adding tetramethoxysilane, tetraethoxysilane, etc., including the case of not adding, can be performed during mixing and heating operations, and Use after a slight reaction.
該等矽烷偶聯劑之中,本發明中較佳使用之矽烷偶聯劑宜為每一分子偶聯劑中具有一個矽原子之化學結構的矽烷偶聯劑。 本發明中,特佳之矽烷偶聯劑可列舉:N-2-(胺基乙基)-3-胺基丙基甲基二甲氧基矽烷、N-2-(胺基乙基)-3-胺基丙基三甲氧基矽烷、N-2-(胺基乙基)-3-胺基丙基三乙氧基矽烷、3-胺基丙基三甲氧基矽烷、3-胺基丙基三乙氧基矽烷、3-三乙氧基矽基-N-(1,3-二甲基-亞丁基)丙胺、2-(3,4-環氧環己基)乙基三甲氧基矽烷、3-環氧丙氧基丙基三甲氧基矽烷、3-環氧丙氧基丙基甲基二乙氧基矽烷、3-環氧丙氧基丙基三乙氧基矽烷、胺基苯基三甲氧基矽烷、胺基苯乙基三甲氧基矽烷、胺基苯基胺基甲基苯乙基三甲氧基矽烷等。處理中特別要求高耐熱性時,Si與胺基之間以芳香族基連結者為較理想。 此外,本發明中,視需要亦可倂用磷系偶聯劑、鈦酸酯系偶聯劑等。Among the silane coupling agents, the silane coupling agent preferably used in the present invention is preferably a silane coupling agent having a chemical structure of one silicon atom in each molecular coupling agent. In the present invention, particularly preferred silane coupling agents include N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, and N-2- (aminoethyl) -3 -Aminopropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyl Triethoxysilane, 3-triethoxysilane-N- (1,3-dimethyl-butylene) propylamine, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, aminophenyl Trimethoxysilane, aminophenethyltrimethoxysilane, aminophenylaminomethylphenethyltrimethoxysilane, and the like. When high heat resistance is particularly required during processing, an aromatic group is preferably connected between Si and the amine group. In addition, in the present invention, a phosphorus-based coupling agent, a titanate-based coupling agent, or the like may be used if necessary.
本發明中之矽烷偶聯劑之塗布方法並無特別限定,可使用一般的濕式塗覆法或於氣相之塗覆法。濕式塗覆法宜使用矽烷偶聯劑之原液或溶劑溶液,較佳為使用醇溶液等,並利用旋塗、毛細管塗布、棒塗、塗抹、模塗、缺角輪塗布、網版印刷、凹版印刷、噴墨印刷、噴塗、噴霧塗布等方法。 本發明中,就該矽烷偶聯劑塗布方法而言,較佳為可使用藉由氣相之氣相塗布法。氣相塗布法係使無機基板曝露於已氣化之矽烷偶聯劑而進行塗布。矽烷偶聯劑塗布可換言之為矽烷偶聯劑處理。氣化係指有矽烷偶聯劑之蒸氣,亦即實質上為氣體狀態之矽烷偶聯劑、或微粒狀態之矽烷偶聯劑存在的狀態。曝露係指使有機系高分子膜接觸包含前述已氣化之矽烷偶聯劑的氣體,或於真空狀態下使有機系高分子膜接觸。The coating method of the silane coupling agent in the present invention is not particularly limited, and a general wet coating method or a coating method in a vapor phase can be used. The wet coating method is preferably a stock solution or a solvent solution of a silane coupling agent, preferably an alcohol solution, etc., and uses spin coating, capillary coating, bar coating, smearing, die coating, corner wheel coating, screen printing, Gravure printing, inkjet printing, spray coating, spray coating and other methods. In the present invention, as for the coating method of the silane coupling agent, a vapor-phase coating method using a gas phase is preferably used. The vapor-phase coating method is performed by exposing an inorganic substrate to a vaporized silane coupling agent. In other words, the silane coupling agent coating can be treated by a silane coupling agent. Gasification refers to the vapor in which the silane coupling agent is present, that is, the state in which the silane coupling agent in a substantially gas state or the particulate silane coupling agent exists. Exposure means that the organic polymer film is brought into contact with a gas containing the aforementioned vaporized silane coupling agent, or the organic polymer film is brought into contact in a vacuum state.
矽烷偶聯劑之蒸氣,可藉由將液體狀態之矽烷偶聯劑加溫到30℃~矽烷偶聯劑之沸點之溫度而輕易地獲得。矽烷偶聯劑之蒸氣於沸點以下亦可生成。也可利用矽烷偶聯劑之微粒共存的狀態。又,也可利用溫度壓力之操作實施提高蒸氣密度之操作。矽烷偶聯劑之沸點取決於化學結構而有所不同,大約為100~250℃之範圍。惟,200℃以上之加熱會有招致矽烷偶聯劑之有機基側之副反應之虞,故不佳。The vapor of the silane coupling agent can be easily obtained by heating the liquid silane coupling agent to a temperature of 30 ° C to the boiling point of the silane coupling agent. The vapor of the silane coupling agent can also be generated below the boiling point. The state in which the fine particles of the silane coupling agent coexist can also be used. In addition, the operation of increasing the vapor density may be performed by the operation of temperature and pressure. The boiling point of the silane coupling agent varies depending on the chemical structure, and is in the range of about 100 to 250 ° C. However, heating at 200 ° C or higher may cause side reactions on the organic side of the silane coupling agent, which is not preferable.
本發明中之矽烷偶聯劑層之厚度宜為5nm以上,為9nm以上較佳,為18nm以上更佳,為45nm以上又更佳。矽烷偶聯劑之膜厚的上限宜為500nm以下,為390nm以下尤佳,為240nm以下又更佳。矽烷偶聯劑之膜厚可藉由疊層體之剖面的電子顯微鏡觀察而測定。The thickness of the silane coupling agent layer in the present invention is preferably 5 nm or more, more preferably 9 nm or more, more preferably 18 nm or more, and more preferably 45 nm or more. The upper limit of the film thickness of the silane coupling agent is preferably 500 nm or less, more preferably 390 nm or less, and even more preferably 240 nm or less. The film thickness of the silane coupling agent can be measured by electron microscope observation of the cross section of the laminate.
將矽烷偶聯劑加溫之環境可為加壓下、常壓下、減壓下中之任一者,欲促進矽烷偶聯劑之氣化時,宜為大約常壓下或減壓下。矽烷偶聯劑大多分類為可燃性液體,故宜於密閉容器內,較佳為將容器內以鈍性氣體置換後再進行氣化作業。 另一方面,考量改善生產效率及減低生產設備價格的觀點,宜於不使用真空之環境塗布矽烷偶聯劑較理想。例如,可在常壓下將有機系高分子膜設置於腔室內,使包含已氣化之矽烷偶聯劑之約常壓的載流氣體充滿腔室內,從使矽烷偶聯劑沉積起,到再次回復至無已氣化之矽烷偶聯劑的狀態為止,於大約大氣壓之狀態進行。The environment in which the silane coupling agent is heated may be any one of under pressure, normal pressure, and reduced pressure. To promote the gasification of the silane coupling agent, it is preferably under normal pressure or reduced pressure. Most of the silane coupling agents are classified as flammable liquids, so they are suitable for sealed containers. It is preferred to replace the inside of the container with a passive gas before performing gasification operations. On the other hand, considering the viewpoint of improving production efficiency and reducing the price of production equipment, it is ideal to apply the silane coupling agent in an environment without using a vacuum. For example, the organic polymer film can be placed in the chamber under normal pressure, so that the carrier gas containing the vaporized silane coupling agent can be filled in the chamber at about normal pressure, from the time when the silane coupling agent is deposited to It returns to the state where there is no vaporized silane coupling agent again, and it is performed at about atmospheric pressure.
可對於成為本發明之聚醯亞胺膜的聚醯亞胺膜之至少與無機基板貼合之側施以下列活化處理:UV臭氧處理、真空電漿處理、大氣壓電漿處理、電暈處理、火燄處理、ITRO處理、酸處理、鹼處理、曝露於活性氣體之處理等。該等處理主要具有將聚醯亞胺膜表面之有機物等附著污染物除去的清潔效果、及使聚醯亞胺膜表面活性化並改善與無機基板之黏接性的效果。The following activation treatment may be applied to at least the side of the polyimide film that becomes the polyimide film of the present invention attached to the inorganic substrate: UV ozone treatment, vacuum plasma treatment, atmospheric piezoelectric plasma treatment, corona treatment, Flame treatment, ITRO treatment, acid treatment, alkali treatment, treatment by exposure to active gas, etc. These treatments mainly have the cleaning effect of removing organic pollutants such as organic matter on the surface of the polyimide film, and the effect of activating the surface of the polyimide film and improving the adhesion to the inorganic substrate.
作為將無機基板與聚醯亞胺膜藉由矽烷偶聯材予以疊層而得之聚醯亞胺/無機基板疊層體之製造方法,宜將塗布有矽烷偶聯劑之無機基板與聚醯亞胺膜重疊,或將無機基板與塗布有矽烷偶聯劑之聚醯亞胺膜重疊,並將兩者藉由加壓而予以疊層。又,亦可對無機基板與聚醯亞胺膜之兩者進行矽烷偶聯劑處理。就加壓方法而言,可列舉於大氣中常溫下或邊施加熱邊進行加壓的通常的壓製、於真空中的壓製。較佳壓力為0.5MPa至20MPa,更佳為2至10MPa。壓力高的話,會有造成基板破損之虞,壓力低的話,有時會有產生不密接之部分的情況。較佳溫度範圍為0℃至550℃,更佳為10℃至300℃。溫度過高的話,會有膜、無機基板劣化的可能性。在真空中進行壓製時,真空度為利用通常的油旋轉泵浦所形成之真空即足夠,若為10Torr以下左右即足夠。As a method for producing a polyimide / inorganic substrate laminate obtained by laminating an inorganic substrate and a polyimide film with a silane coupling material, it is preferable to apply the inorganic substrate coated with a silane coupling agent and the polyfluorene. The imine film is overlapped, or the inorganic substrate and the polyfluorene imide film coated with a silane coupling agent are overlapped, and the two are laminated by pressing. Alternatively, both the inorganic substrate and the polyfluorene film may be treated with a silane coupling agent. Examples of the pressing method include ordinary pressing under normal temperature in the air or applying heat while applying heat, and pressing in a vacuum. The preferred pressure is 0.5 MPa to 20 MPa, and more preferably 2 to 10 MPa. If the pressure is high, the substrate may be damaged, and if the pressure is low, a non-tight part may be generated. The preferred temperature range is 0 ° C to 550 ° C, and more preferably 10 ° C to 300 ° C. If the temperature is too high, the film and the inorganic substrate may deteriorate. When pressing in a vacuum, the degree of vacuum is sufficient to be a vacuum formed by an ordinary oil rotary pump, and it is sufficient if it is about 10 Torr or less.
又,亦可暫時先疊層,然後藉由熱處理使密接穩定化。此時的熱處理溫度,宜於50℃~550℃之範圍進行。更佳為100℃~500℃之範圍。可藉由熱處理來改善密接穩定性。為50℃以下的話,會有密接穩定性改善的效果小的傾向,超過550℃的話,會有聚醯亞胺膜發生熱劣化的傾向。Alternatively, it may be laminated for a while, and then the adhesion may be stabilized by heat treatment. The heat treatment temperature at this time is preferably performed in a range of 50 ° C to 550 ° C. More preferably, it is in the range of 100 ° C to 500 ° C. Heat treatment can be used to improve adhesion stability. If it is 50 ° C or lower, the effect of improving the adhesion stability tends to be small, and if it exceeds 550 ° C, the polyimide film tends to be thermally deteriorated.
又,聚醯亞胺膜及無機基板之疊層體之製造方法,亦可採用如下之方法:使前述聚醯亞胺或聚醯亞胺之前驅體溶解於有機溶劑而得之溶液流延至無機基板上,然後藉由加熱處理形成聚醯亞胺膜。溶劑只要是可溶解聚醯亞胺或聚醯亞胺之前驅體即可,可理想地使用非質子性極性溶劑等。例如可列舉:N,N-二甲基甲醯胺、N,N-二甲基乙醯胺、N,N-二乙基乙醯胺、N,N-二甲基甲氧基乙醯胺等N,N-二低級烷基羧基醯胺類、N-甲基-2-吡咯烷酮、N-乙基-2-吡咯烷酮、二甲基亞碸、二甲基碸、1,3-二甲基-2-咪唑啶酮、γ-丁內酯、二乙二醇二甲醚、間甲酚、六甲基磷醯胺、N-乙醯基-2-吡咯烷酮、乙基賽珞蘇乙酸酯、二乙二醇二甲醚、環丁碸、對氯苯酚等。此外,溶劑亦可為2種以上之混合物。In addition, the method for producing a laminate of a polyimide film and an inorganic substrate may also employ the following method: a solution obtained by dissolving the aforementioned polyimide or a polyimide precursor in an organic solvent is cast to an inorganic A polyimide film is formed on the substrate by heat treatment. The solvent may be any solvent capable of dissolving polyimide or a precursor of polyimide, and an aprotic polar solvent or the like is preferably used. Examples include: N, N-dimethylformamide, N, N-dimethylacetamide, N, N-diethylacetamide, N, N-dimethylmethoxyacetamide N, N-di-lower alkylcarboxyfluorenamines, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, dimethylsulfinium, dimethylfluorene, 1,3-dimethyl -2-imidazolidinone, γ-butyrolactone, diethylene glycol dimethyl ether, m-cresol, hexamethylphosphamidamine, N-ethylfluorenyl-2-pyrrolidone, ethylcythreon acetate , Diethylene glycol dimethyl ether, cyclobutane, p-chlorophenol, etc. The solvent may be a mixture of two or more kinds.
用以使聚醯亞胺前驅體醯亞胺化之加熱處理之條件並無特別限定,至少於150℃~200℃,更佳為160℃至190℃之溫度範圍加熱處理10分鐘以上,較佳為30分鐘以上,特佳為60分鐘以上,然後於最高溫度為400℃~550℃,較佳為430℃~530℃,更佳為460℃~530℃之溫度範圍進行加熱處理較佳。此外,於200℃以上之溫度進行加熱處理的時間(亦包括於最高溫度進行加熱處理的時間)可適當決定,並無特別限定。藉由該處理,可使溶劑蒸發,並形成聚醯亞胺,可製造良好的聚醯亞胺/無機基板疊層體。The conditions for the heat treatment for making the polyfluorene imide precursor sulfonimide are not particularly limited. The temperature is at least 150 ° C to 200 ° C, more preferably 160 ° C to 190 ° C, and the heat treatment is more than 10 minutes, preferably It is preferably 30 minutes or more, particularly preferably 60 minutes or more, and then heat treatment is preferably performed in a temperature range of 400 ° C to 550 ° C, preferably 430 ° C to 530 ° C, and more preferably 460 ° C to 530 ° C. In addition, the time for which the heat treatment is performed at a temperature of 200 ° C. or higher (including the time for which the heat treatment is performed at the highest temperature) can be appropriately determined and is not particularly limited. By this treatment, the solvent can be evaporated to form a polyimide, and a good polyimide / inorganic substrate laminate can be produced.
又,亦可為如下之方法:將前述聚醯亞胺或聚醯亞胺之前驅體溶解於有機溶劑而得之溶液塗布在無機基板上,視情形進行部分乾燥,於其上疊層聚醯亞胺膜,之後進行乾燥。又,也可採用如下之公知的方法:將前述聚醯亞胺或聚醯亞胺之前驅體溶解於有機溶劑而得之溶液塗布在無機基板上,視情形進行部分乾燥,進一步,將不同種類之聚醯亞胺或聚醯亞胺之前驅體溶解於有機溶劑而得之溶液塗布在無機基板上,之後進行乾燥等。Alternatively, the following method may also be used: a solution obtained by dissolving the aforementioned polyimide or polyimide precursor in an organic solvent is coated on an inorganic substrate, and partially dried as appropriate, and a polyfluorene is laminated thereon The imine film is then dried. Alternatively, a known method may be adopted in which a solution obtained by dissolving the aforementioned polyimide or polyimide precursor in an organic solvent is coated on an inorganic substrate, and partially dried as appropriate, and further, different types A solution obtained by dissolving polyimide or a polyimide precursor in an organic solvent is coated on an inorganic substrate, and then dried.
本發明中之泡罩,係指聚醯亞胺膜及無機基板之疊層體中,在聚醯亞胺膜與無機基板之間產生空隙,聚醯亞胺膜側隆起成帳蓬狀、或穹窿狀之形狀的缺點。 本發明之泡罩係指能以肉眼確認之尺寸者。更具體而言,係指將於平面方向觀察到之泡罩設為圓時直徑為50μm以上者。此外,此處就直徑而言,泡罩變形時係長徑與短徑之平均值。The blister in the present invention refers to a laminate of a polyimide film and an inorganic substrate, and a gap is generated between the polyimide film and the inorganic substrate, and the side of the polyimide film bulges into a tent shape, or Disadvantage of dome-like shape. The blister of the present invention refers to a size that can be confirmed with the naked eye. More specifically, it refers to a blister having a diameter of 50 μm or more when the blister viewed in a planar direction is round. In addition, the diameter here is an average value of the long diameter and the short diameter when the blister is deformed.
本發明之聚醯亞胺膜及無機基板之疊層體,高度為3μm以上之泡罩之個數宜為每1平方米10個以下,為7個以下更佳,為4個以下尤佳,為2個以下又更佳。為0個又尤佳。 本發明中,進一步,高度為2.2μm以上之泡罩之個數宜為每1平方米10個以下,為7個以下更佳,為4個以下尤佳,為2個以下又更佳。為0個又尤佳。 本發明中,進一步,高度為1.4μm以上之泡罩之個數宜為每1平方米10個以下,為7個以下更佳,為4個以下尤佳,為2個以下又更佳。為0個又尤佳。 本發明中,進一步,高度為0.8μm以上之泡罩之個數宜為每1平方米10個以下,為7個以下更佳,為4個以下尤佳,為2個以下又更佳。為0個又尤佳。 本發明中之泡罩總數之個數密度宜為50個/平方米以下。In the laminate of the polyimide film and the inorganic substrate of the present invention, the number of the blister having a height of 3 μm or more is preferably 10 or less per 1 square meter, more preferably 7 or less, and particularly preferably 4 or less. It is even better for 2 or less. 0 is even better. In the present invention, further, the number of blister having a height of 2.2 μm or more is preferably 10 or less per 1 square meter, more preferably 7 or less, even more preferably 4 or less, and even more preferably 2 or less. 0 is even better. In the present invention, further, the number of the blister having a height of 1.4 μm or more is preferably 10 or less per 1 square meter, more preferably 7 or less, more preferably 4 or less, even more preferably 2 or less. 0 is even better. In the present invention, further, the number of the blister having a height of 0.8 μm or more is preferably 10 or less per 1 square meter, more preferably 7 or less, particularly preferably 4 or less, and even more preferably 2 or less. 0 is even better. The number density of the total number of blister in the present invention is preferably 50 pieces / square meter or less.
本發明中之泡罩之高度可利用3D雷射顯微鏡進行測定。本發明中之泡罩缺點部分之高度之平均值宜為2μm以下,為1.6μm以下更佳,為1.2μm以下尤佳,為0.8μm以下又更佳。泡罩缺點部之高度之平均值超過該範圍的話,製造產能會明顯降低。The height of the blister in the present invention can be measured using a 3D laser microscope. The average value of the height of the shortcomings of the blister in the present invention is preferably 2 μm or less, more preferably 1.6 μm or less, even more preferably 1.2 μm or less, and even more preferably 0.8 μm or less. If the average value of the height of the defect part of a blister exceeds this range, manufacturing capacity will fall significantly.
本發明中,泡罩個數密度(個/平方米)與泡罩之平均高度(μm)的乘積宜為20以下。泡罩之高度係決定本發明之疊層體之品質的重要要素,高度低之泡罩有多數個時,算出的泡罩高度之平均值會較低。但,藉由求出泡罩之平均高度與泡罩個數分布的乘積,可成為對於可撓性器件製造產能改善係有效的參數。In the present invention, the product of the number density of the blister (number / square meter) and the average height of the blister (μm) is preferably 20 or less. The height of the blister is an important factor that determines the quality of the laminated body of the present invention. When there are many blisters with a low height, the average value of the calculated blister height is low. However, by calculating the product of the average height of the blister and the distribution of the number of blister, it can be an effective parameter for improving the productivity of flexible device manufacturing.
本發明中之泡罩尤其涉及於前述空隙內包有碳化物粒子(碳化物異物)的泡罩。碳化物係指為黑色或黑褐色,且滿足SEM-EDX中C元素與O元素之合計相對於全部元素為超過50%之情形、或顯微IR分析中呈現碳化物特有之光譜之情形中之至少任一條件的物質。 使用玻璃板作為無機基板時,藉由從玻璃板側觀察,可輕易地識別所內包之異物(粒子)的顏色。不透明的無機基板的情況,可將膜側切開進行觀察。The blister in the present invention particularly relates to a blister in which carbide particles (carbide foreign matter) are enclosed in the gap. Carbide refers to the case where the carbide is black or black-brown and satisfies the total of C and O elements in the SEM-EDX to more than 50% of all elements, or in the case where a spectrum specific to carbides is present in micro-IR analysis Substances with at least any of the conditions. When a glass plate is used as the inorganic substrate, the color of the foreign matter (particles) contained in it can be easily identified by looking from the glass plate side. In the case of an opaque inorganic substrate, the film side can be cut and observed.
本發明之聚醯亞胺膜及無機基板之疊層體,可藉由將聚醯亞胺膜與無機基板製成疊層體後,於350℃以上未達600℃之溫度進行熱處理而獲得。熱處理溫度的下限宜為370℃以上,為390℃以上更佳,為420℃以上尤佳。又,熱處理溫度的上限宜為560℃以下,為520℃以下更佳,為490℃以下尤佳,為460℃以下又更佳。熱處理溫度未達預定之範圍時,有時會有異物之碳化不會充分進行的情況,又,熱處理溫度為預定之範圍以上的話,容易產生聚醯亞胺膜劣化,可撓性器件從基板剝離時膜發生破裂等的問題。 關於熱處理的時間,可在加熱並達到預定溫度後保持5秒以上,較佳為保持30秒以上,尤佳為保持100秒以上後進行冷卻。保持時間延長到超過必要的話,聚醯亞胺膜容易發生劣化。 關於升溫速度,宜以5℃/分鐘~200℃/分鐘之升溫速度進行加熱。此外,以200℃/分鐘以上之速度升溫的話,有時會有泡罩之個數增加的情況。The laminated body of the polyimide film and the inorganic substrate of the present invention can be obtained by making the polyimide film and the inorganic substrate into a laminated body, and then performing a heat treatment at a temperature of 350 ° C. to 600 ° C. The lower limit of the heat treatment temperature is preferably 370 ° C or higher, more preferably 390 ° C or higher, and even more preferably 420 ° C or higher. The upper limit of the heat treatment temperature is preferably 560 ° C or lower, more preferably 520 ° C or lower, even more preferably 490 ° C or lower, and even more preferably 460 ° C or lower. When the heat treatment temperature is not within a predetermined range, carbonization of foreign substances may not be sufficiently performed. If the heat treatment temperature is above the predetermined range, the polyimide film may be easily deteriorated, and the flexible device may be peeled from the substrate. Problems such as film breakage occur. The heat treatment time can be maintained for 5 seconds or more after heating and reaching a predetermined temperature, preferably for 30 seconds or more, and even more preferably for 100 seconds or more before cooling. If the holding time is longer than necessary, the polyimide film is liable to deteriorate. Regarding the heating rate, heating is preferably performed at a heating rate of 5 ° C / minute to 200 ° C / minute. In addition, when the temperature is raised at a rate of 200 ° C./min or more, the number of blister may increase.
本發明中,將聚醯亞胺膜與無機基板製成疊層體後,於350℃以上未達600℃之溫度進行熱處理,宜在熱處理後以10℃/分鐘以上、90℃/分鐘以下之速度冷卻到至少200℃。冷卻速度宜為15℃/分鐘以上,尤佳為25℃/分鐘以上。又,冷卻速度的上限宜為80℃/分鐘以下,為70℃/分鐘以下更佳,為60℃/分鐘以下又更佳。 [實施例]In the present invention, after the polyimide film and the inorganic substrate are made into a laminate, heat treatment is performed at a temperature of 350 ° C to 600 ° C. Cool down to at least 200 ° C. The cooling rate is preferably 15 ° C / min or more, particularly preferably 25 ° C / min or more. The upper limit of the cooling rate is preferably 80 ° C / min or less, more preferably 70 ° C / min or less, and even more preferably 60 ° C / min or less. [Example]
以下,舉實施例及比較例對本發明進行更加具體地說明,但本發明並不限定於下列實施例。此外,下列實施例中之物性的評價方法、處理方法、操作方法等如下。Hereinafter, the present invention will be described more specifically with examples and comparative examples, but the present invention is not limited to the following examples. In addition, the evaluation methods, processing methods, operation methods, and the like of the physical properties in the following examples are as follows.
<聚醯胺酸之還原黏度(ηsp/C)> 針對聚合物溶解於N-甲基-2-吡咯烷酮(或N,N-二甲基乙醯胺)使聚合物濃度成為0.2g/dl的溶液,使用烏氏(Ubbelohde)型黏度管於30℃進行測定(聚醯胺酸溶液之製備使用之溶劑為N,N-二甲基乙醯胺時,係使用N,N-二甲基乙醯胺溶解聚合物並進行測定。)< Reduction viscosity of polyamidic acid (ηsp / C) > The polymer is dissolved in N-methyl-2-pyrrolidone (or N, N-dimethylacetamide) to make the polymer concentration 0.2 g / dl. The solution was measured using an Ubbelohde-type viscosity tube at 30 ° C. (The solvent used in the preparation of the polyfluorinated acid solution was N, N-dimethylacetamide. Phenamine dissolves the polymer and measures it.)
<聚醯亞胺膜之膜厚> 針對聚醯亞胺膜,利用疊層體剖面之SEM剖面觀察而求出。此外,除非另有說明,否則係將在距各聚醯亞胺膜之端部1mm以上內側的區域中隨機選出的5點之膜厚的平均值作為聚醯亞胺膜之膜厚。 至於第2聚醯亞胺膜,係求出從層合前之聚醯亞胺膜或將第2聚醯亞胺膜從疊層體進行90度剝離後之膜隨機選出的10點之算術平均值,以作為膜厚。又,由任意10點之膜厚的最大值、最小值、算術平均值,依下式算出膜厚不均[%]。 膜厚不均=100×(最大值-最小值)/算術平均值 [%] 此外,為第2聚醯亞胺膜的聚醯亞胺膜之厚度,係利用觸針式膜厚計進行測定。 又,可良好地剝離時,剝離後之聚醯亞胺膜之膜厚、膜厚不均,和層合前之聚醯亞胺膜之膜厚及膜厚不均幾乎一致。<Film thickness of polyimide film> The polyimide film was obtained by observing the SEM cross section of the cross section of the laminate. In addition, unless otherwise stated, an average value of film thicknesses of 5 points randomly selected in a region 1 mm or more inside from the end of each polyimide film is used as the film thickness of the polyimide film. As for the second polyimide film, an arithmetic average of 10 points was randomly selected from the polyimide film before lamination or the film after the second polyimide film was peeled 90 degrees from the laminate. Value as the film thickness. In addition, the film thickness unevenness [%] was calculated from the maximum, minimum, and arithmetic mean of the film thickness at any 10 points according to the following formula. Film thickness unevenness = 100 × (maximum value-minimum value) / arithmetic average value [%] In addition, the thickness of the polyimide film of the second polyimide film is measured by a stylus film thickness meter . In addition, when the film can be peeled well, the film thickness and film thickness unevenness of the polyimide film after peeling are almost the same as the film thickness and film thickness unevenness of the polyimide film before lamination.
<熱分解溫度> 將已從疊層板剝離之聚醯亞胺膜(聚醯亞胺膜)作為試樣,於150℃乾燥30分鐘後,依下列條件進行熱重量測定(TGA),將試樣之質量減少5%時之溫度作為熱分解溫度。 裝置名 :MAC science公司製TG-DTA2000S 盤 : 鋁盤(非氣密型) 試樣質量 : 10mg 升溫開始溫度 : 30℃ 升溫速度 : 20℃/min 環境 : 氬氣<Thermal decomposition temperature> A polyimide film (polyimide film) peeled from the laminate was used as a sample, and after drying at 150 ° C for 30 minutes, the thermogravimetric measurement (TGA) was performed under the following conditions. The temperature at which the sample mass was reduced by 5% was taken as the thermal decomposition temperature. Device name: TG-DTA2000S plate manufactured by MAC science company: Aluminum plate (non-air-tight type) Sample mass: 10mg Heating start temperature: 30 ° C Heating rate: 20 ° C / min Environment: Argon
<線膨脹係數> 針對以聚醯亞胺膜(膜)形式獲得之試樣,依下列條件測定伸縮率,測定30℃~45℃、45℃~60℃、…之15℃之間隔的伸縮率/溫度,實施該測定直到300℃,算出全部測定值之平均值作為CTE。 設備名 : MAC science公司製TMA4000S 試樣長度 : 20mm 試樣寬度 : 2mm 升溫開始溫度 : 25℃ 升溫結束溫度 : 400℃ 升溫速度 : 5℃/min 環境 : 氬氣<Linear expansion coefficient> For a sample obtained in the form of a polyimide film (film), the stretch ratio is measured under the following conditions, and the stretch ratio at intervals of 30 ° C to 45 ° C, 45 ° C to 60 ° C, ... at 15 ° C is measured. This temperature was measured at 300 ° C, and the average value of all measured values was calculated as CTE. Device name: MAC science company TMA4000S Sample length: 20mm Sample width: 2mm Heating start temperature: 25 ° C Heating end temperature: 400 ° C Heating speed: 5 ° C / min Environment: Argon
<泡罩缺點之個數> 計數能以肉眼確認之泡罩個數。可檢測到之泡罩的尺寸以平均徑計為50μm以上。 <泡罩缺點之高度測定> 聚醯亞胺膜及無機基板之疊層體的泡罩部分(凸缺點)之高度,係利用Keyence製彩色3D雷射顯微鏡VK9710之高度測定功能進行測量。<Number of blister defects> Count the number of blister that can be confirmed with the naked eye. The size of the detectable blister is 50 μm or more in terms of average diameter. <Measurement of height of blister defect> The height of the blister part (convex defect) of a laminate of a polyimide film and an inorganic substrate is measured using the height measurement function of a color 3D laser microscope VK9710 manufactured by Keyence.
<矽烷偶聯劑層之厚度> 利用聚醯亞胺膜及無機基板之疊層體之剖面的電子顯微鏡照片來測量厚度。<Thickness of Silane Coupling Agent Layer> The thickness was measured using an electron microscope photograph of a cross section of a laminated body of a polyimide film and an inorganic substrate.
<異物分析> 將內部含有異物之泡罩部分的聚醯亞胺膜切開,實施異物的顯微IR測定,獲得之IR光譜的吸收整體上平緩且寬廣,於1000-3500cm-1 之區域未確認到來自樹脂之特徵吸收,確認係碳化物。<Foreign matter analysis> The polyimide film of the blister part containing the foreign matter was cut open, and the micro IR measurement of the foreign matter was performed. The absorption of the obtained IR spectrum was smooth and broad as a whole, and it was not confirmed in the region of 1000-3500 cm -1 The characteristic absorption from the resin was confirmed to be a carbide.
<製造例> [聚醯亞胺前驅體(聚醯胺酸)溶液PV1的製造] 將配備有氮氣導入管、溫度計、攪拌棒之反應容器內進行氮氣置換,然後,加入5-胺基-2-(對胺基苯基)苯并唑223質量份、N,N-二甲基乙醯胺4416質量份,使其完全溶解後,加入均苯四甲酸二酐217質量份,於25℃之反應溫度攪拌24小時,得到褐色且黏稠的聚醯胺酸溶液[PV1]。<Manufacturing example> [Production of polyimide precursor (polyamic acid) solution PV1] Nitrogen substitution was performed in a reaction vessel equipped with a nitrogen introduction tube, a thermometer, and a stirring rod, and then 5-amino-2 was added. -(P-aminophenyl) benzo 223 parts by mass of azole and 4,416 parts by mass of N, N-dimethylacetamidamine were completely dissolved, and then 217 parts by mass of pyromellitic dianhydride was added and stirred at a reaction temperature of 25 ° C for 24 hours to obtain a brown and viscous Polyfluorinated acid solution [PV1].
[聚醯亞胺前驅體(聚醯胺酸)溶液PV2的製造] 將配備有氮氣導入管、溫度計、攪拌棒之反應容器內進行氮氣置換,然後,將作為四羧酸二酐之3,3’,4,4’-聯苯四羧酸二酐398質量份、對苯二胺132質量份、4,4’-二胺基二苯醚30質量份溶解於4600質量份之N,N-二甲基乙醯胺,於25℃之反應溫度攪拌24小時,得到褐色且黏稠的聚醯胺酸溶液[PV2]。[Manufacturing of Polyimide Precursor (Polyamidine) Solution PV2] The reaction vessel equipped with a nitrogen introduction tube, a thermometer, and a stirring rod was replaced with nitrogen, and then 3,3 as tetracarboxylic dianhydride 398 parts by mass of ', 4,4'-biphenyltetracarboxylic dianhydride, 132 parts by mass of p-phenylenediamine, and 30 parts by mass of 4,4'-diaminodiphenyl ether were dissolved in 4,600 parts by mass of N, N- Dimethylacetamide was stirred at a reaction temperature of 25 ° C. for 24 hours to obtain a brown and viscous solution of polyamidic acid [PV2].
[聚醯亞胺前驅體(聚醯胺酸)溶液PV3的製造] 將配備有氮氣導入管、溫度計、攪拌棒之反應容器內進行氮氣置換,然後,將均苯四甲酸酐545質量份、4,4’-二胺基二苯醚500質量份溶解於8000質量份之N,N-二甲基乙醯胺,於將溫度保持在20℃以下之狀態同樣使其進行反應,得到聚醯胺酸溶液[PV3]。 [聚醯亞胺前驅體(聚醯胺酸)溶液PV4的製造] 將配備有氮氣導入管、溫度計、攪拌棒之反應容器內進行氮氣置換,然後,將均苯四甲酸二酐545質量份、對苯二胺153質量份、4,4’-二胺基二苯醚200質量份溶解於8000質量份之N,N-二甲基乙醯胺,於將溫度保持在20℃以下之狀態同樣使其進行反應,得到聚醯胺酸溶液[PV4]。[Production of polyimide precursor (polyamic acid) solution PV3] The reaction vessel equipped with a nitrogen introduction tube, a thermometer, and a stirring rod was replaced with nitrogen, and then 545 parts by mass of pyromellitic anhydride, 4 500 parts by mass of 4'-diaminodiphenyl ether was dissolved in 8,000 parts by mass of N, N-dimethylacetamidamine, and the same reaction was performed while keeping the temperature below 20 ° C to obtain polyamidoamine Acid solution [PV3]. [Production of polyimide precursor (polyamic acid) solution PV4] Nitrogen substitution was performed in a reaction vessel equipped with a nitrogen introduction tube, a thermometer, and a stirring rod, and then 545 parts by mass of pyromellitic dianhydride, 153 parts by mass of p-phenylenediamine and 200 parts by mass of 4,4'-diaminodiphenyl ether are dissolved in 8,000 parts by mass of N, N-dimethylacetamidamine, and the same conditions are maintained at a temperature below 20 ° C. This was reacted to obtain a polyamidic acid solution [PV4].
[聚醯亞胺前驅體(聚醯胺酸)溶液PV5的製造] 將配備有氮氣導入管、溫度計、攪拌棒之反應容器內進行氮氣置換,然後,在反應容器中氮氣環境下加入2,2’-二甲基-4,4’-二胺基聯苯155.9質量份與N,N-二甲基乙醯胺1200質量份,使其溶解後,邊將反應容器冷卻邊直接以固體的形態分次添加環丁烷四羧酸二酐142.9質量份,於室溫攪拌5小時。之後,利用N,N-二甲基乙醯胺1000質量份進行稀釋,得到還原黏度4.20dl/g之聚醯胺酸溶液[PV5]。[Manufacturing of Polyimide Precursor (Polyamino Acid) Solution PV5] Nitrogen substitution was performed in a reaction vessel equipped with a nitrogen introduction tube, a thermometer, and a stirring rod, and then 2, 2 were added to the reaction vessel under a nitrogen atmosphere. 155.9 parts by mass of '-dimethyl-4,4'-diaminobiphenyl and 1200 parts by mass of N, N-dimethylacetamidamine, after dissolving them, directly cooling the reaction vessel in a solid form 142.9 parts by mass of cyclobutanetetracarboxylic dianhydride was added in portions, and the mixture was stirred at room temperature for 5 hours. Thereafter, it was diluted with 1000 parts by mass of N, N-dimethylacetamide to obtain a polyamic acid solution [PV5] having a reduction viscosity of 4.20 dl / g.
[聚醯亞胺前驅體(聚醯胺酸)溶液PV6的製造] 將配備有氮氣導入管、溫度計、攪拌棒之反應容器內進行氮氣置換,然後,在反應容器中氮氣環境下加入2,2’-二(三氟甲基)-4,4’-二胺基聯苯176.5質量份與N,N-二甲基乙醯胺1200質量份,使其溶解後,邊將反應容器冷卻邊直接以固體的形態分次添加1,2,4,5-環己烷四羧酸二酐122.9質量份,於室溫攪拌18小時。之後,利用N,N-二甲基乙醯胺500質量份進行稀釋,得到還原黏度3.26dl/g之聚醯胺酸溶液[PV6]。[Manufacturing of Polyimide Precursor (Polyamino Acid) Solution PV6] The reaction vessel equipped with a nitrogen introduction tube, a thermometer, and a stirring rod was replaced with nitrogen, and then, 2, 2 was added to the reaction vessel under a nitrogen atmosphere. 176.5 parts by mass of '-bis (trifluoromethyl) -4,4'-diaminobiphenyl and 1200 parts by mass of N, N-dimethylacetamide, after dissolving them, directly cooling the reaction vessel while cooling 122.9 parts by mass of 1,2,4,5-cyclohexanetetracarboxylic dianhydride was added in portions as a solid, and stirred at room temperature for 18 hours. Thereafter, it was diluted with 500 parts by mass of N, N-dimethylacetamide to obtain a polyamic acid solution [PV6] having a reduction viscosity of 3.26 dl / g.
[聚醯亞胺前驅體(聚醯胺酸)溶液PV7的製造] 將配備有氮氣導入管、溫度計、攪拌棒之反應容器內進行氮氣置換,然後,將作為四羧酸二酐之3,3’,4,4’-聯苯四羧酸二酐398質量份、對苯二胺148質量份溶解於4600質量份之N,N-二甲基乙醯胺,於25℃之反應溫度攪拌24小時,得到褐色且黏稠的聚醯胺酸溶液[PV7]。[Production of polyimide precursor (polyamic acid) solution PV7] The reaction vessel equipped with a nitrogen introduction tube, a thermometer, and a stirring rod was replaced with nitrogen, and then 3,3 as a tetracarboxylic dianhydride 398 parts by mass of ', 4,4'-biphenyltetracarboxylic dianhydride and 148 parts by mass of p-phenylenediamine dissolved in 4,600 parts by mass of N, N-dimethylacetamide, and stirred at a reaction temperature of 25 ° C. for 24 Hours, a brown and viscous solution of polyamidic acid [PV7] was obtained.
<聚醯亞胺膜的製造> 將製造例中獲得之聚醯胺酸溶液[PV1]消泡後,使用缺角輪塗布機塗布於東洋紡(股)公司製聚酯膜A4100之平滑面,利用連續式乾燥機於乾燥溫度95℃乾燥5分鐘,於110℃乾燥10分鐘,製成聚醯胺酸膜。然後,將獲得之聚醯胺酸膜從聚酯膜剝離,利用銷固持膜的兩端,以連續式熱處理爐於250℃熱處理3分鐘,於485℃熱處理3分鐘,冷卻至室溫,得到聚醯亞胺膜[PF1a]。獲得之聚醯亞胺膜的評價結果顯示於表1。表中之「薄膜成膜」表示使用藉由該方法獲得之聚醯亞胺膜。 以下,變更聚醯胺酸溶液、成膜方法、塗布膜厚、乾燥、熱處理條件,並同樣進行溶液成膜,得到表1所示之聚醯亞胺膜。結果顯示於表1。<Production of Polyimide Film> The polyamic acid solution [PV1] obtained in the production example was defoamed, and then applied to a smooth surface of a polyester film A4100 made by Toyobo Co., Ltd. using a corner wheel coater, and used The continuous dryer was dried at 95 ° C for 5 minutes and 110 ° C for 10 minutes to prepare a polyamine film. Then, the obtained polyamic acid film was peeled from the polyester film, and both ends of the film were used to heat-treat in a continuous heat treatment furnace at 250 ° C for 3 minutes, and then heat-treated at 485 ° C for 3 minutes, and cooled to room temperature to obtain a polymer film. Imine film [PF1a]. The evaluation results of the obtained polyfluoreneimide film are shown in Table 1. The "film formation" in the table indicates that a polyimide film obtained by this method is used. Hereinafter, the polyimide solution, film formation method, coating film thickness, drying, and heat treatment conditions were changed, and the solution was film-formed in the same manner to obtain a polyimide film shown in Table 1. The results are shown in Table 1.
<無機基板(支持體)> 基板[G1]係使用370mm×470mm、厚度0.7mm之液晶顯示器用玻璃板。 基板[G2]係使用550mm×650mm、厚度0.7mm之液晶顯示器用玻璃板。<Inorganic substrate (support)> The substrate [G1] is a glass plate for a liquid crystal display using 370 mm × 470 mm and a thickness of 0.7 mm. The substrate [G2] is a glass plate for a liquid crystal display using 550 mm x 650 mm and a thickness of 0.7 mm.
<UV/臭氧處理> 使用Lantechnical Service公司製UV/臭氧洗淨改質裝置,將燈與無機基板的距離設定為30mm,對無機基板實施1分鐘的UV/臭氧處理。<UV / ozone treatment> A UV / ozone cleaning and reforming device manufactured by Lantechnical Service was used, the distance between the lamp and the inorganic substrate was set to 30 mm, and the inorganic substrate was subjected to UV / ozone treatment for 1 minute.
<矽烷偶聯劑處理> 將配備有加熱板與無機基板之支持台的腔室用潔淨的乾燥氮氣置換後,將已施以UV/臭氧處理之無機基板設置於支持台,以使液面位於無機基板之200mm下方的方式,放置裝滿有矽烷偶聯劑(3-胺基丙基三甲氧基矽烷)之淺盤,利用加熱板將淺盤加熱至100℃,使無機基板之下表面曝露於矽烷偶聯劑蒸氣3分鐘,然後從腔室取出,設置在潔淨操作台內,以使無機基板之與曝露面為相反的側接觸熱板的方式載置於已調溫至120℃之加熱板,實施1分鐘的熱處理,以進行矽烷偶聯劑處理。〈Silane coupling agent treatment〉 After replacing the chamber of the support table equipped with a heating plate and an inorganic substrate with clean dry nitrogen, the UV / ozone-treated inorganic substrate is set on the support table so that the liquid surface is positioned on the support table. In the manner of 200 mm below the inorganic substrate, a shallow pan filled with a silane coupling agent (3-aminopropyltrimethoxysilane) was placed, and the shallow pan was heated to 100 ° C with a hot plate to expose the lower surface of the inorganic substrate. After the silane coupling agent vapor for 3 minutes, then take it out of the chamber, set it in a clean operation table, and place it on a heating that has been adjusted to 120 ° C so that the side of the inorganic substrate opposite to the exposed surface contacts the hot plate. The plate was subjected to a heat treatment for 1 minute to perform a silane coupling agent treatment.
<膜的洗淨處理> 將獲得之聚醯亞胺膜利用連續式濕式膜洗淨裝置予以洗淨,進一步,邊運送邊在120℃之潔淨乾燥空氣中保持5分鐘以進行再乾燥。此外,將濕式洗淨裝置中使用之洗淨液藉由膜過濾進行精製直到電阻率成為15MΩ・cm以上,然後,利用臭氧產生器所生成的含臭氧之潔淨空氣進行曝氣,將臭氧濃度調整成為10ppm以上。<Washing Treatment of Film> The obtained polyimide film was washed with a continuous wet film cleaning device, and further dried in a clean and dry air at 120 ° C for 5 minutes while being transported. In addition, the cleaning liquid used in the wet cleaning device is refined by membrane filtration until the resistivity becomes 15 MΩ ・ cm or more, and then the ozone-containing clean air generated by the ozone generator is used to aerate the ozone concentration. It is adjusted to 10 ppm or more.
<電漿處理> <膜的電漿處理> 將聚醯亞胺膜裁切成比起玻璃基板之長邊、短邊各小10mm之尺寸,利用單片式真空電漿裝置實施處理。真空電漿處理係採用使用了平行平板型電極之RIE模式、利用RF電漿的處理,於真空腔室內導入氮氣,並導入13.54MHz的高頻電力,處理時間為3分鐘。<Plasma treatment> <Plasma treatment of film> The polyimide film is cut to a size 10 mm smaller than each of the long and short sides of the glass substrate, and the treatment is performed using a single-piece vacuum plasma device. The vacuum plasma processing system adopts the RIE mode using parallel plate electrodes and RF plasma processing. Nitrogen is introduced into the vacuum chamber, and 13.54MHz high-frequency power is introduced. The processing time is 3 minutes.
<氣體阻隔層的形成:氮化矽薄膜> 利用通常的電漿CVD裝置並依下列方法形成氣體阻隔層。原料氣體係使用矽烷氣(SiH4 )、氨氣(NH3 )、氮氣(N2 )、及氫氣(H2 )。關於各種氣體之供給量,矽烷氣設定為100sccm,氨氣設定為200sccm,氮氣設定為500sccm,氫氣設定為500sccm,成膜壓力設定為60Pa。所供給之電漿設定為於13.58MHz之3000W。成膜過程中對玻璃板(基板支架)供給於頻率400kHz之500W的偏壓電力。<Formation of Gas Barrier Layer: Silicon Nitride Film> A gas barrier layer was formed using a conventional plasma CVD apparatus in the following manner. The source gas system uses silane gas (SiH 4 ), ammonia gas (NH 3 ), nitrogen gas (N 2 ), and hydrogen gas (H 2 ). Regarding the supply amounts of various gases, the silane gas was set to 100 sccm, the ammonia gas was set to 200 sccm, the nitrogen gas was set to 500 sccm, the hydrogen gas was set to 500 sccm, and the film formation pressure was set to 60 Pa. The supplied plasma was set to 3000W at 13.58MHz. During the film formation process, a glass plate (substrate holder) was supplied with a bias power of 500 W at a frequency of 400 kHz.
[表1]
此外,表1中之簡稱如下。 PMDA:均苯四甲酸二酐、 BPDA:3,3’,4,4’-聯苯四羧酸二酐、 CBA:環丁烷四羧酸二酐、 CHA:1,2,4,5-環己烷四羧酸二酐、 ODA:4,4’-二胺基二苯醚、 PDA:苯二胺、 DAMBO:5-胺基-2-(對胺基苯基)苯并唑、 BPA:2,2’-二甲基-4,4’-二胺基聯苯、 FA:2,2’-二(三氟甲基)-4,4’-二胺基聯苯、 CTE:線膨脹係數。The abbreviations in Table 1 are as follows. PMDA: pyromellitic dianhydride, BPDA: 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride, CBA: cyclobutanetetracarboxylic dianhydride, CHA: 1,2,4,5- Cyclohexanetetracarboxylic dianhydride, ODA: 4,4'-diaminodiphenyl ether, PDA: phenylenediamine, DAMBO: 5-amino-2- (p-aminophenyl) benzo Azole, BPA: 2,2'-dimethyl-4,4'-diaminobiphenyl, FA: 2,2'-bis (trifluoromethyl) -4,4'-diaminobiphenyl, CTE: coefficient of linear expansion.
<實施例1> 對成為聚醯亞胺膜之聚醯亞胺膜[PF1a]實施電漿處理,以重疊於已施以矽烷偶聯劑處理之無機基板之矽烷偶聯劑處理面的方式將聚醯亞胺膜予以重疊,利用輥層合機進行暫時壓接後,設置在潔淨操作台內,以使無機基板側接觸熱板的方式載置於已調溫至150℃之加熱板,實施3分鐘的熱處理,得到聚醯亞胺膜及無機基板之疊層體。將獲得之聚醯亞胺膜及無機基板之疊層體於溫度20~25℃、相對濕度65±30%之環境下保存12小時以上。<Example 1> The polyimide film [PF1a], which is a polyimide film, was subjected to a plasma treatment, and the silane coupling agent-treated surface of the inorganic substrate treated with the silane coupling agent was superposed. The polyimide film was superimposed, and after temporary compression bonding with a roller laminator, it was installed in a clean operation table, and the inorganic substrate side was brought into contact with the hot plate, and the plate was placed on a heating plate that had been adjusted to 150 ° C, and implemented. The heat treatment was performed for 3 minutes to obtain a laminate of a polyimide film and an inorganic substrate. The obtained laminate of the polyimide film and the inorganic substrate was stored in an environment at a temperature of 20 to 25 ° C. and a relative humidity of 65 ± 30% for more than 12 hours.
將獲得之聚醯亞胺膜及無機基板之疊層體在450℃之鈍性烘箱中實施30分鐘的熱處理。從烘箱中取出,以使無機基板(玻璃板)側接觸的方式放置於另外準備的已調溫至25℃以上180℃以下之間之預定溫度的銅板上,快速冷卻至200℃以下之溫度。冷卻速度係以銅板之溫度進行控制。將從450℃冷卻至200℃時之平均冷卻速度作為冷卻速度。The obtained laminate of polyimide film and inorganic substrate was heat-treated in a blunt oven at 450 ° C for 30 minutes. Take it out of the oven, place it on the copper substrate that has been adjusted to a predetermined temperature between 25 ° C and 180 ° C so that the inorganic substrate (glass plate) side is in contact, and quickly cool it to a temperature below 200 ° C. The cooling rate is controlled by the temperature of the copper plate. The average cooling rate when cooling from 450 ° C to 200 ° C was taken as the cooling rate.
將存在於獲得之聚醯亞胺膜及無機基板之疊層體的泡罩個數以各尺寸分級計數。進一步,將泡罩總數除以疊層體面積而求出個數密度。進一步,利用雷射顯微鏡測定全部泡罩之高度,求取其平均值,並求出泡罩之平均高度與個數密度的乘積。選出任意5個經計數之泡罩,將聚醯亞胺膜側切開,對所內包之異物粒子進行分析。結果確認到均為碳化物粒子。 以上結果顯示於表2。此外,表2、表3、表4中,鈍性係表示於經氮氣置換之環境下的處理。又,尺寸50μm-1mm意指50μm以上未達1mm,尺寸1-2mm意指1mm以上未達2mm,尺寸2-3mm意指2mm以上3mm以下。The number of blister existing in the obtained laminated body of the polyimide film and the inorganic substrate was counted in steps of each size. Furthermore, the number density was calculated by dividing the total number of blister by the area of the laminate. Furthermore, the height of all the blister was measured with a laser microscope, the average value was calculated | required, and the product of the average height of the blister and the number density was calculated | required. Select any 5 counted blister, cut the polyimide film side, and analyze the foreign particles contained in it. As a result, it was confirmed that all of them were carbide particles. The above results are shown in Table 2. In addition, in Table 2, Table 3, and Table 4, inertness shows the process in the environment substituted with nitrogen. A size of 50 μm to 1 mm means 50 μm or more and less than 1 mm, a size of 1-2 mm means 1 mm to 2 mm, and a size of 2-3 mm means 2 mm to 3 mm.
<實施例2~9、比較例1~6> 以下,適當變更無機基板、聚醯亞胺膜、各自之處理條件等並且進行實驗,得到表2、表3、表4所示之實施例2~實施例9、比較例1~6之聚醯亞胺膜及無機基板之疊層體。存在於各疊層體之泡罩之高度分布顯示於表2、表3、表4。此外,與實施例1同樣針對各疊層體選出任意5個泡罩,對泡罩之內包物進行分析,確認到內包物均為碳化物粒子。<Examples 2 to 9 and Comparative Examples 1 to 6> Experiments were performed by appropriately changing the inorganic substrate, the polyimide film, and the respective processing conditions, etc., to obtain Example 2 shown in Tables 2, 3, and 4. ~ A laminate of the polyfluorine film and the inorganic substrate of Example 9 and Comparative Examples 1 to 6. The height distribution of the blister present in each laminate is shown in Table 2, Table 3, and Table 4. In addition, in the same manner as in Example 1, five blisteres were selected for each laminate, and the contents of the blister were analyzed, and it was confirmed that the contents were all carbide particles.
[表2]
[表3]
[表4]
<應用實施例> 將實施例1~9、比較例1~6中獲得之聚醯亞胺膜及無機基板之疊層體於100℃乾燥1小時,然後,設置於形成氣體阻隔層之真空裝置並進行減壓。確認達到預定的真空度後,在聚醯亞胺膜之表面形成氮化矽薄膜作為氣體阻隔層。然後,於積層體之氣體阻隔層之表面,以10-5 Pa量級之真空度蒸鍍各薄膜並予以疊層。首先,於成膜溫度400℃形成膜厚100nm之由銦・錫氧化物(ITO)構成之陽極。之後,在ITO上形成30nm之厚度的N,N’-二(1-萘基)-N,N’-二苯基聯苯胺),於其上形成10nm之厚度的1,3-雙(N-咔唑基)苯。然後,從不同的蒸鍍源將下列化合物1與4,4’-雙(N-咔唑基)-1,1’-聯苯進行共蒸鍍,形成20nm之厚度的層,製成發光層。此時,化合物1之濃度為10重量%。然後,形成40nm之厚度的1,3,5-參(1-苯基-1H-苯并咪唑-2-基)苯,於其上真空蒸鍍0.8nm之氟化鋰。進一步,同樣形成ITO,製成陰極。在其上進一步形成氣體阻隔層。最後從玻璃板剝下,藉此製作可撓性有機EL元件。 針對獲得之有機EL元件,目視判定發光元件的品質,以一邊為10cm之正方形換算的黑點(無發光點)為1個以下時評價為◎,為3個以下時評價為○,為4個以上時評價為×。 結果顯示於表2、表3、表4。 由結果可知:使用本發明之聚醯亞胺膜及無機基板之疊層體的話,可製作良好的器件。 [化1][產業上利用性]<Application Example> The laminated body of the polyimide film and the inorganic substrate obtained in Examples 1 to 9 and Comparative Examples 1 to 6 was dried at 100 ° C for 1 hour, and then installed in a vacuum device for forming a gas barrier layer. And decompressed. After confirming that the predetermined degree of vacuum was reached, a silicon nitride film was formed on the surface of the polyimide film as a gas barrier layer. Then, on the surface of the gas barrier layer of the laminated body, each thin film is vapor-deposited with a degree of vacuum of the order of 10 -5 Pa and laminated. First, an anode made of indium tin oxide (ITO) with a film thickness of 100 nm was formed at a film formation temperature of 400 ° C. Then, N, N'-bis (1-naphthyl) -N, N'-diphenylbenzidine) was formed on ITO to a thickness of 30 nm, and 1,3-bis (N -Carbazolyl) benzene. Then, the following compounds 1 and 4,4'-bis (N-carbazolyl) -1,1'-biphenyl were co-evaporated from different evaporation sources to form a layer having a thickness of 20 nm, and a light-emitting layer was prepared. . At this time, the concentration of Compound 1 was 10% by weight. Then, 1,3,5-ginseng (1-phenyl-1H-benzimidazol-2-yl) benzene was formed to a thickness of 40 nm, and lithium fluoride of 0.8 nm was vapor-deposited thereon. Further, ITO was formed in the same manner to form a cathode. A gas barrier layer is further formed thereon. Finally, it was peeled from the glass plate, thereby fabricating a flexible organic EL element. With regard to the obtained organic EL element, the quality of the light-emitting element was visually judged, and when the black point (no light-emitting point) converted to a square of 10 cm on one side was 1 or less, it was evaluated as ◎, when it was 3 or less, it was evaluated as ○ and as 4 In the above case, it was evaluated as ×. The results are shown in Tables 2, 3 and 4. From the results, it can be seen that a good device can be produced by using the laminate of the polyfluorene imide film and the inorganic substrate of the present invention. [Chemical 1] [Industrial availability]
如上述所示,本發明之疊層體可理想地用作用以製作可撓性顯示元件等可撓性電子器件之基板。本發明可廣泛用於各種可撓性電子器件、MEMS元件、感測器元件、太陽能電池、穿戴式用元件等。As described above, the laminated body of the present invention is ideally used as a substrate for manufacturing flexible electronic devices such as flexible display elements. The present invention can be widely used in various flexible electronic devices, MEMS elements, sensor elements, solar cells, wearable elements, and the like.
1‧‧‧無機基板1‧‧‧ inorganic substrate
2‧‧‧聚醯亞胺膜2‧‧‧Polyimide film
3‧‧‧異物(碳化物粒子)3‧‧‧ Foreign matter (carbide particles)
h‧‧‧泡罩高度(凸缺點高度)h‧‧‧ height of blister (convex height)
w‧‧‧泡罩尺寸(泡罩徑)w‧‧‧ blister size (blister diameter)
[圖1]圖1係本發明之聚醯亞胺膜及無機基板之疊層體中之泡罩的概略說明圖。[Fig. 1] Fig. 1 is a schematic explanatory view of a blister in a laminated body of a polyimide film and an inorganic substrate according to the present invention.
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WO2020226062A1 (en) * | 2019-05-09 | 2020-11-12 | 三菱瓦斯化学株式会社 | Layered body |
KR20240058836A (en) * | 2021-09-02 | 2024-05-07 | 도요보 가부시키가이샤 | laminate |
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WO2012050072A1 (en) * | 2010-10-13 | 2012-04-19 | 東洋紡績株式会社 | Polyimide film, method for manufacturing same, and method for manufacturing layered product |
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JP6067740B2 (en) * | 2012-11-08 | 2017-01-25 | 旭化成株式会社 | Flexible device manufacturing method, laminate, manufacturing method thereof, and resin composition |
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